MXPA97004198A - Fibrilas functionalizes - Google Patents

Abstract

Graphitic nanotubes including tubular fullerenes and fibrils are presented, which are functionalized by chemical substitution or adsorption of functional portions. More specifically, the invention relates to graphitic nanotubes that are uniformly or uniformly substituted with chemical moieties or on which certain cyclic compounds and complex structures containing such functionalized fibrils bound together are adsorbed. The invention also relates to methods for the introduction of functional groups on the surface of such fibril

Description

FIBRILAS EU CTONALIZA ñS. FIELD DF THE INVENTION l -i μr-e ™, efd e? Nven > ~ íAn = > e t-ef i ere in terms- getiHi-dl íi -t 1: 1 n Lu o-? iji'f f (l íi. -;, un i 'i uyf "ny 1 f ili'-il i-, fn- J orial i -.' ^ d -» ??? di - »nl nUi i fcu i ò i.ii n.-to well μor ds> .M 1.1 OH of μor ione fu i > tria 3 e- >, fl't-i e-.μen. í fim in, 1 fef lürf ii ? r? your t? -? > _)! - '•' f í t i > : o- = > um fot-memenle or cíii no um f rinemen te ÍU¿ t i lie i > Jo =, 'on fXji--. i ie--? u f mu. = * - > or b > H *? - > pb »'e l UII HU r ie Lo-. 1 (< > 'tipie - ^ l, cyclical: - ^ tii bert and -? _ Refierier which contain t leb f ibri la- :, futtc i ort * I i-ada = &gs; enl a ra en en la-la, L i nvenc io n = e To enter a group "in -i 3 e < = > in 1 iiiiper? i? i? ~ > 'Je L -.- le = > fii la -: -. n ANTFCEDFNTES HF THE INVENTION E = 3>: a invention in-e finds out from the entbi what the- », f ib ila * gr-d f í bi Read = &tt onn '! • - 'ree trinen L e V ^ IJ G, I a -> f' br il -i •> de> -i rb> jr? o -ijft 'le ór > J Lo -i de > ~ - < i 'of'ii ye.'¡¡. t .. i .1 ar > -1-. qu t iene dj ?? n L? * os "ii ltfei (Ot - = J 1" ¡¡¡i, from pl t- fm ell > - i r-fet ittlVí -li ". ,, 1-!. y > .ji¡ yi - i rio - i '? r¡ major of p ef e iai nferi te "a C)" 2 u "F., i -d en in' -HI 'UI for - = > and Inri > id > "'μreμ i rj' =? d i before -.?;t.n-t?μ?j-, go l ólt 'Z * t -i l í L i > "a e v I '"' 1 > > »IJ? -j • > ue '> Mil lñt t -H'b '' .i e -üifii-'i f ii iH-. mel -i 1 h i. =,. TI] H depó.? i > > ~ > and i J I-! 1 (HI i - »i ~ ie- 'ir' 'l. -tei tli (Ai e e electron microscopy A good initial review and reference is found in Baker and Harris, Chemistry and' Physics of Carbon, alker and Thrower ed., Vol.14, 1978, page 83, which is incorporated herein by reference, see also Rodriguez, N., J. Mater, Research, vol.8, page 3233 (1993), which is incorporated herein by reference. In 1976, Endo et al. (see Obelin, A. and Endo, M., J. of Crystal Growth, vol, 32 (1976), pp. 335-349, which is incorporated herein by reference) elucidated the mechanism It is seen that they originated from a metallic catalyst particle that, in the presence of a hydrocarbon-containing gas, is supersaturated with carbon.A cylindrical ordered graphitic core is extruded which immediately, According to Endo et al., it is covered with an external layer of graphite deposited pyrolically, these fibrils with an ionic pyrol coating have typically diameters greater than 0.1 μ, more typically between 0.2 and f.5 μ. Ert 1983, Tennent, in the North American patent no. No. 4,663,230, which is incorporated herein by reference, managed to grow cylindrical ordered graphite cores, not contaminated with pyrolytic carbon. Accordingly, Tennent's invention provided access to fibrils of smaller diameters, typically 35 to 700 angstroms (0.0035 to 0.070 μ) and to a graffiti surface "in the co-or grown" state, ordered. Fibrillar carbons of a perfect ñßnos structure but also without an outer layer of pyrolytic carbon also grew. The fibrils, fullerenes and nanofibers operated in this application are distinguished from commercially available continuous carbon fibers or reinforcing materials. In contrast to fibrils, which have desirably large but inevitably finite aspect ratios, continuous carbon fibers have aspect ratios (Length / Diameter) of at least 10,000 and frequently 1,000,000 or more. The diameter of the continuous fibers is also much greater than the diameter of the fibrils, always above 1.0 μ and typically between 5 and 7 μ. Continuous carbon fibers are made by pyrolysis of organic precursor fibers, usually rayon, pal iacri loni tri lo (PAN) and tar. Accordingly, they may include heteroatoms within their structure. The graphite nature of the continuous "as-processed" carbon fibers varies, but they can be subjected to a subsequent graphing step. Differences in the degree of graphitization, orientation and crystallinity of the graphite planes, if present, the potential presence of heteroatoms and even the absolute difference in substrate diameter make the experience with continuous fibers a limited predictor of the chemistry of the nanofibras .: Tennent, in the North American patent no. No. 4,663,230 discloses free carbon fibrils of a continuous thermal carbon coating and has numerous graphitic outer layers substantially parallel to the axis of the fibril. As such they can be characterized as having their axes c, the axes that are perpendicular to the tangents of the graphite curved layers, substantially perpendicular to their cylindrical axes. They generally have diameters not greater than 0.1 μ and proportions between the diameter length of at least 5. Desirably they are substantially free of a continuous thermal carbon coating, i.e., pyrolitically deposited carbon resulting from the thermal decomposition of the gas fed used to prepare them. Tennent et al., In U.S. Pat. No. 5,171,560, which is incorporated herein by reference, discloses carbon fibrils free from thermal coating and having graffiti layers substantially parallel to the axes of the fibrils such that the projection of said layers on said fibril shafts extends over a distance of at least two diameters of fibril. Typically, such fibrils are substantially cylindrical graphitic nanophones of a substantially constant diameter and comprise cylindrical graphite sheets whose axes c are substantially perpendicular to their cylindrical axis. They are substantially free of carbon deposited piratically, have a diameter of less than 0.1 μ, have a ratio of length to diameter greater than 5, These fibrils are of primary interest in the invention. Additional details regarding the formation of carbon fibril aggregates can be found in the presentation by Snyder et al., Nartea and icana patent application no. of series 149,573, filed on January 28, 1988, and the PCT application no. US89 00322, filed on January 28, 1989 ("carbon fibrils") WO 89/07163, and today et al., US patent application no. series -3-13,837, filed September 28, 1989, and PCT application number US90 / 05498, filed on September 27, 1990 ("Fibril Aggregates and Methods for Making Them") WO 91/05089, which is incorporated by reference in its entirety. they all assign to the same assignee as the present invention which are incorporated herein by reference. Moy et al., In USSN 07 / 887,307 filed May 22, 1992, which is incorporated herein by reference, discloses separate fibrils as aggregates having various macroscopic morphologies (as determined by scanning electron microscopy), wherein they are randomly entangled between them to form tangled fibril balls that resemble bird nests ("BN"); or with aggregates consisting of bundles of straight or slightly bent or twisted carbon fibrils having their tanc and the same relative orientation, and having the appearance of combed yarn ("CY") for example, the longitudinal axis of each fibril (in spite of individual folds or retrofits) extends in the same direction as the direction of the adjacent fibrils in the bundles; or, as aggregates consisting of straight to slightly bent or twisted fibrils that are tangled loosely together to form an "open network" ("ON") structure. In open network structures, the degree of fibril entanglement is greater than that observed in combed thread aggregates (where individual fibrils have substantially the same relative orientation) but less than the entanglement of bird nests. Read additions CY and ON are more easily dispersed than DN making them useful in composite manufacturing, where uniform properties are desired throughout the structure. When the projection of the graphite layers on the axis of the fibrils extends over a distance less than two diameters of fibril, the carbon planes of the graphitic nanofiber, in section, to the appearance of a fishbone. These are known as fishbone fibrils, Geu, in US Patent no. No. 4,855,091, which is incorporated herein by reference, provides a process for the preparation of fish-fiber fibrils. Try free of pyrolytic coating. These fibrils are also useful in the practice of the invention. Carbon nonotubes of a morphology similar to the catalytically grown fibrils described above grew in a carbon arc at elevated temperature (Iijima, Na ture 354 56 1991). It is now generally accepted (Weaver, Science 265 1994) that these nanofibers that grew in arc have the same morphology as the previous fibrils that grew catically from Tennent. The carbon nanofibers that grew in arc are also useful in the innovation. Maccarthy et al, in US Patent Application Serial No. 3 1,967 filed May 15, 1989, which is incorporated herein by reference, describe processes for oxidizing the surface of carbon fibrils that include contacting the fibrils with an oxidizing agent including sulfuric acid (H2SO4) and potassium chlorate (KCl03) under reaction conditions (eg time, temperature and pressure) sufficient to oxidize the surface of the fibril. Fibrils oxidized according to the McCarthy et al. they are oxidized in a non-uniform manner, that is, the carbon atoms are substituted with a mixture of carbonyl, aldehyde, ketone, phenol groups and other carbonyla groups. Fibrils have also been non-uniformly oxidized by treatment with nitric acid. International Application PCT / US94 / 10168 discloses the formation of oxidized fibrils containing a mixture of functional groups. Hoogenvaad, M.S., et al. ("Metal catalysts supported in a Novel Carbon Support", Presented at the Sixth International Conference on the Scientific Basis for the Preparation of Heterogeneous Catalysts, Brussels, Belgium, September 1994) also found that it was beneficial in the preparation of precious metals supported in fibrils, first oxidize the surface of fibrils with nitric acid. Pretreatment with acid is a standard step in the preparation of noble metal catalysts supported on carbon where, given the usual sources of such carbon, it serves both to clean the surface of undesirable materials and to function it. In published work, McCarthy and Benipg (Polymer Preprints ACS Di. Of Polymer Chem. 30 (1) 420 (1990)) prepared derivatives of oxidized fibrils to demonstrate that the surface comprises several oxidized groups. The compounds that they prepared, f m Ih i dragons, esters of the roertic, talose salts, etc., were selected because of their analytical utility, for example, bright color, or because they present some other strong and easily identified and iferen iada signal. These compounds were not isolated and, unlike the derivatives described here, have no practical importance. While many uses were found for carbon fibrils and carbon fibril aggregates, as described in the aforementioned patents and patent applications, many different and important uses can develop if the fibril surfaces are operated. Functional func- tion, whether uniform or non-uniform, allows the interaction of func- tional fibrils with several substrates to form unique compositions of matter with unique properties and allows the generation of fibrila structures in b links between the functional sites in the surfaces of the fibrils. OBJECTS OF THE INVENTION It is therefore a primary object of this invention to provide functional fibrils, ie, fibrils whose surfaces are uniformly or not uniformly modified such that they have a functional chemical moiety associated therewith. A further and related object of this invention is to provide fibrils whose surfaces are operated by reaction with oxidizing means or other chemical means. It is a further and related object of this invention to provide fibrils whose surfaces are uniformly modified either by means of a chemical reaction or by means of physical absorption of species which themselves have a chemical reactivity. It is an additional object to provide fibrils whose surfaces have been modified, for example, by oxidation, which are then modified adi cially by reaction with functional groups. It is a further and related object of this invention to provide fibrils whose surfaces are modified with a spectrum of functional groups in such a way that the fibrils can chemically react or can be physically bound and chemical groups in vr-ios substrates It's another additional object <; The present invention provides complex structures of fibrils by linking functional groups on the fibrils together from a range of chemical linkers. It is a further related object of this invention to provide methods for the chemical modification of fibril surfaces and methods for the physical absorption of species on the surface of fibrils to provide, in each case, a functional portion associated with the surface of the fibrils. the fibril. It is a further object of this invention to provide new co-factors of matter based on fibr the functionalities. DETAILED DESCRIPTION OF THE INVENTION These and other objects of the invention are achieved in compositions that have in general the formula (CnHL * Rm where n is an integer number, L is a number less than O.ln, is a number less than 0.5 n, each of P is the same and is selected within S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', S? R'3, Si -0B '~ * -yR'3-y, Si -tO-Si P' 2 -0R ', R ", Li, A1P'2, Hg- X, T1Z2 and Mg-X, and is a number or integer equal to or less than 3, P 'is alkyl, aryl, cycloalkyl or aralkyl, R "is f luoroa Iqui lo, fluoroaryl, f luoroc icloa lqu i lo, f 1 uoroa a ltjt.ii 1 oo either cyclaaryl, X is h luro, and Z is carboxylate or tif 1 uraoacetata. The carbon atoms, Cn, are surface carbons of a graphitic nanotube, a cylindrical substance of a substantially constant diameter. Nartotubes include those that have a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, preferably less than 0.1 μ, Nanotubes are also graphitic nanotubes 1 cylindrical substance, substantially free of > The deposition of the material, with a greater degree of preference, or nanotubes, was made by having a projection of the graphite layers on the axis of the fibers, which = > e extends over a distance of at least two diameters of fibril and / or those having cylindrical graphitic sheets whose axes c are substantially perpendicular to their cylindrical axis. These compositions are uniform to the extent that each P is the same. Nanotubes not uniformly substituted were also prepared. These include compositions of the formula (CnHL ^ Rm where rt, L, m, P and the nanotube itself are as defined above, provided that each of P does not contain oxygen, or, if each of P is a group It contains oxygen, COOH is not present, N-inotubos works with 1 ions that have the formula (CnHL + Pm where rt, L,, R and R 'have the same meaning as before and lo = carbon atoms are atoms The surface carbon is a fish fibril that has a ratio between the length and the diameter greater than 5, is also included within the invention, these may be uniformly or not uniformly substituted, preferably the nanotubes are Thermally resistant faces have diameters of less than 0.5 μ In the invention, also fungal ions are included which have 1 fórmula formula (CnHL-WP'-R) m where n, L, m, R 'and P have the meanings indicated above: carbon atoms, Cn, are carbon s supe fi iales of a substantially cylindrical graphitic nanotube of a constant lucent constant diameter. The nanotubes have a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, preferably less than 0.1 μ. The nanotubes can be nanotubes substantially free of carbon deposited pi rolically. With greater preference, the naootuhos are two in which the layer of the layers of gr-ifi L on the fibers of the fibers is spread over a distance of at least two fibril diameters and / or those that have inductive graphite sheets whose c axes are substantial. Try perpendicular to the cylindrical axis. Both the nanotubes substituted uniformly and non-uniformly react the super fi cial atoms Crt. The majority of the carbon atoms in the surface layer of a graphitic fibril, as in graphite, are basic planar carbons. The flat carbons b salts are relatively inert to chemical attack. At deflection sites where, for example, the graphite plane is not eroded completely around the fibril, there are carbon atoms analogous to the carbon atoms of a graphite plane (see Urry, Ele entary Equilibrium Che istry of Coal, Wiley, Nem Yorfc 1989) for a discussion of the edge plane and basal carbons). At defect sites, the edge plane or basal carbons of the lower, inner layers of the nanotube may be exposed. The term surface carbon includes all the carbons, of basal plane and edge, of the outermost layer of the nanotube, as well as the carbons, both of the basal plane and / or edge, of the lower layers that may be placed in the defect sites of the outermost layer. The edge carbons react and must contain some heteroatom or group to satisfy the valence of the carbon. The substituted nanotubes described above can func on ona 1 ize ad ic iona Try profitably. Such compositions include compositions of the formula (CnHL-H-Am where the carbons are surface carbons of a nanotube, n, L, and are as previously described, A is selected from OO 0 0 IIII 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY O CY, And the appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, an oly g >; < nu > If an antigen, either an enzyme substrate, an enum inhibitor or the transition state analogue of an enzyme substrate is selected, it is selected ßnfcre R'-OH, R'-NH2, R'SH, R'CHO, R'CN, R'X, R'SiR'3, R'Si «0- SiR'2 * OR ', R'-R", R'-N-CO, (C ^ O * ^ , 4C3H6O JH, "C2H40) w- R '" (C3H60) wR' and R ', and w is an integer greater than l and less than 200. The carbon atoms, Cn, are surface carbons of a cylindrical, suspectic, nanotube of cylindrical diameter with a constant diameter. The nanotubes include those that have a ratio between the length and the upper diameter n 5 and a diA l. i nfer i or -t O.l μs preferably less than 0.05 μ. The nanotubes can also be graphitic nanotubes, 1 cylindrical substances, substantially free of deposited carbon. More preferably, they are characterized by having a projection of the graphite layers in the fibrils that are spread over a distance, that of at least two diameters of fibril and / or fibrils. They are made of cylindrical graffiti whose c and c are substances that are perpendicular to their cylindrical e. Preferably, the nanotubes are free of thermal coating and have diameters less than 0.5 u. The-; Functional funnels of the structure (CnHI WP '-P) m can also be canvas funnels for producing compositions having the formula iNHL (R' -A) m where n, L,, P 'and A are as defined above. The carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic nanotube of a substantially constant diameter. Nartotubes include those having a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, preferably less than O.l, or nanotubes can also be graphitic nanotubes, = > They are also cylindrical, substantially free of carbon deposited p ictically. With greater degree of preference, they are characterized by having a projection of the graphite layers on the axes of the fibrils that extends over a distance of at least two diameters of fibril and / or having cylindrical graphitic sheets whose c-axes are sust. Normally perpendicular 3 its cylindrical axis. Preferably, the nanotubes are free of thermal imidesting and have diameters less than 0.5 μ. The compositions of the present invention also include nartotubes on which certain cyclic compounds are adsorbed. These include subject components of the íCrtHL ^ - íX-Pa) m where n is an integer, L is a number less than O.ln, nor is less than 0.5n, a is zero. or a number less than 10, X is a polynuclear aromatic moiety, a heteronuclear poly aromatic moiety or an aromatic moiety m * -ta lopol i eteron? c read r and P is as previously reported. The carbon atoms Cn, are superficial carbons of a nanometer, its cylindrical tan, with a substantially constant diameter. The nanotubes include those having a ratio between the length and the diameter super lor 3 5 and a diameter lower than 0.5 μ, preferably less than O.l μ. The nanotubes can also be graphical nanotubes. , their ancillary, illicit, carbon-free substances deposited, with a greater degree of preference, those ac cessed by having a projection of the graphite layers in said fibril axes. which extend over a distance of at least two fibril diameters and / or which have cylindrical graphitic sheets whose e is c are substantially perpendicular to their ilindrical axes. Preferably, the naves are free of thermal coating and have diameters less than 0.5 μ.

The preferred cylindrical compounds are flat acros in accordance with what is described on page 76 of Cotton and Will.nsou, Advanced Organic Chemicals (Advanced Organic Chemistry). The most preferred cyclic compounds for adsorption are the porphyrins and the phosphates. The adsorbed cyclic compounds can be functionalized. Such compositions include compounds of the formula (CnHL * (X-Aa) m where m, rt, L, a, X and A are as defined above and the carbons are surface carbons of a 1 cylindrical substance graphitic nanotube segelen described above, the fungal carbon fibrils in accordance with the above described can in order to be in a matrix. Preferably, the matrix is an organic polymer (for example, a thermosetting resin such as an epoxy resin, of b i a lei a, pol lide, or pali; a thermoplastic resin or a resin molded by reaction injection; or an elastomer such as, for example, natural rubber, rubber, styrene-butadiene, or cis-1,4-polybutylene); an inorganic polymer (for example, polymeric inorganic oxide such as glass), a metal (for example lead or copper), or a ceramic material (for example Portland cement). Without subjecting ourselves to any particular theory, fungal fibrils are better dispersed in polymeric systems because the modified surface properties are more cohesive. The polymer or the modified functional groups (particularly hydrophilic or amine groups) are bonded directly onto the polymer as terminal groups. In this way, polymer systems such as polycarbonate, polyurethane, polyesters, or polylaids / imides are bonded directly onto the fibrils, making the fibrils easier to disperse with better adhesion. The invention is also in relation to methods for introducing functional groups on the surface of carbon fibril by contacting carbon fibrils with a strong oxidizing agent for a period of time sufficient to oxidize the surface of said fibers. fibrils and puts into contact said fibrils with appropriate reactive urt to add a functional group to the oxidized surface. In a preferred embodiment of the present invention, the oxidizing agent is formed from a solution of an alkali metal chlorate in a strong acid. In other embodiments of the invention, the alkali metal lorate is sodium chlorate or potassium chlorate. In preferred embodiments, the strong acid employed is sulfuric acid. Sufficient periods of time for 1-oxidation are approximately 0.5 hours to approximately 24 hours. The invention also relates to methods for the production of carbon fibrils which comprises contacting carbon fibrils with an oxidizing agent for a sufficient period of time to oxidize the surface of the carbon fibrils. , the contacting of surface-oxidized carbon fibrils with suitable reagent to add a functional group to the surface of carbon fibrils, and the additional contacting of surface functionalized fibrils with an effective cross-linking agent to produce a network of carbon fibrils. A preferred crosslinking agent is a polyol, polya ida or p l i acid. ar bo. 11 ico. Functional fibrils are also useful for rigid fibril preparations. A well-dispersed three-dimensional network of fibrils funeted by acid can, for example, be stabilized by crosslinking the acid groups dnterf ibri) with polyols or polyamines to form a rigid network. The invention also includes three-dimensional networks formed by linking functionalized fibrils of the invention. These complexes include at least two fungal fibrils linked by one or more linkers comprising a direct bond or a chemical moiety.

E- > The networks comprise porous media of remarkably uniform equivalent pore size. They are useful as adsorbents, catalyst supports, and media. Although the interstices between these fibrils are irregular both in size and shape, they can be considered as pores and characterized by the methods used to characterize the media. porous The size of the interstices in such networks can be controlled by the concentration and level of dispersion of fibrils, and the concentration and chain lengths of the crosslinking agents. Such materials can act as structured catalyst supports and can be prepared to exclude or include molecules of 5 ci Ho size. From conventional industrial catalysis, they have special applications as large pore supports for biologically insulated vessels. Rigid networks can also serve as a structure in < ") b io i ethic systems for molecular recognition, systems have been deciphered in U.S. Patent No. 5,110.83", and in International Patent Publication No. W093 / 19344. Appropriate selections for crosslinking agents and complexing agents allow for the establishment of specific molecular structures.

METHODS FUNCTIONAL FARO IZAR FIBRILAS The fibrils uniformly funeled by the invention can be prepared directly by sulphonation, addition of elefofil on surfaces of deoxygenated surfaces or metalization. When nanofibers that grew in arc are used, they may require extensive purification before the operation. Ebbesen et al. (Nature 367 519 (1994)) provide a method for purification. Preferably, the carbon fibrils are processed before they are brought into contact with the func tioning agent. Such processing may include dispersing the fibrils in a solvent. In such cases, carbon fibrils can be filtered and dried before further contact. 1. THE FONATION The background of the technique is described in March, J.P., Ad vaneen Organic Chemistry, (Advanced Organic Chemistry), 3rd. edition, Wiley, New Yor * i, 1985; House; H., Modern Synthetie Reactions, (Modern Synthetic Reactions), 2nd. edition, Be jami n / Cummings, Menlo Par! , CA 1 * 972. Activated C-H bonds (including aromatic C-H) can be sulfonated using fuming sulfuric acid (pi r-osul furic acid), which is a concentrated sulfuric acid solution containing up to 20% S03. The convention method is by means of the liquid phase at a temperature of approximately 80 * C using p i rosul acid; however, activated C-H bonds can also be sulphonated using S03 in aprotic, inert solvents or S03 in the vapor phase. The reaction is: -C-H + SP3 - > -C-S03H The overreaction results in the formation of sulfones, in accordance with the reaction: 2-C-H + SP3 > -C-S02-C- + H20 EXAMPLE 1 Activation of C-H bonds using Sulfuric Acid Reactions were performed in the gas phase and in solution without any difference in ignition in terms of results. The reaction in the vapor phase was carried out in a reactor of a water reactor heated by a furnace i i d ertj. A multi-neck row containing S03 to 'A in H2S04 concentrate equipped with gas inlet / outlet tube = was used as a source of S03. A weighted example of fibril (BN or CC) in a porcelain container was placed in the 2.54 cm tube equipped with a gas inlet. The outlet was connected to a concentrated H2S04 bubble apparatus trap. It was purged with argon in the reactor for 20 minutes to remove all the air, and the sample was heated at 300 ° C for 1 hour to remove residual moisture. After drying, the temperature was adjusted to reaction temperature under an argon atmosphere. When the desired temperature was stabilized, the S03 source was connected to the reactor tube and an argon current was used to carry the S03 vapors from the quartz reactor. The reaction was carried out for the desired time at the desired temperature, after which the reactor was cooled with argon flows. The fibrils were then dried at 90 ° C and in a vacuum of 12.7 cm Hg to obtain the weight gain in the dry state. The sulphonic acid content (-S03H) was determined by the reaction with 0.100N NaOH and a new titration was carried out with 0.100N HCl using oH 6.0 co or end point. The liquid phase reaction was carried out in concentrated sulfoic acid containing% S03 in a 100 c multi-neck flask equipped with a thermometer / temperature controller and a magnetic stirrer. A fibril paste in concentrated H2SO4 (50) was placed in the flask. The acid solution p i rasu 1 f rich C2 <; zc was preheated to approximately 60 * C before its addition to the rea tor. After the reaction, the acid paste was emptied with ice or ice, and diluted immediately with one liter of water. The solids were filtered and washed thoroughly with deionized water until no change in the pH of the wash effluent was observed. The fibrils were dried at 100 ° C under a vacuum of 12.7 cm Hg. Due to the loss of transfer upon filtering, precise weight gains could not be obtained. The results appear in Table 1. Table I Summary of reactions EXAMPLE NO. OF P.EACC SHOWS TYPE OF TEMPERATURE TIME EXPERIMENT peso.q. FIBRILA IN ßC 1A 118-60A Vap 0.20 CY 110 15 m IB 118-61A Vap 0.20 BN 100 30 m 1C 118-61B Vap 0.20 BN 65 15 ID lie-56A Liq 1.2 CY 50 10 m 1E 118-56B Liq 1.0 CY 25 20 m ETEMPL0 NO. WEIGHT GAIN CONCENTRATIONS OF DRY S03H meq / q. 1 9.3% 0.50 IB 8.5% 0.31 1C 4.2% 0.45 ID 0.33 1 E O.40 No significant difference was observed in sulphuric acid content between the reaction in the vapor phase or in the liquid phase. An effect of temperature was observed. A higher reaction temperature (f is steam) provides higher amounts of sulfonis. In 118-61B, the gain of 4.2% by weight corresponded to the sulfonic acid content (theoretically O. 51 meq / g). Experiments 60A and 61A showed too high a weight gain so that it can be assigned only to the sulfonic acid content. It was therefore considered that appreciable amounts of sulfones were also developed. 2. ADDITIONS TO THE SURFACES OF FIBRILLS EXEMPT FROM OXIDE In Urry, G., Elementary Equilibrium Chemistry of Carbon (Chemistry of Elemental Balance of Carbon), Wiley, New York, 1989, background techniques are described. The superficial carbons in the fibrils behave like graphite, that is, they are arranged in hexagonal sheets containing both basal plane carbons or edge carbons. While flat-carbon carbons are relatively inert to chemical attacks, the edge carbons are reactive and must contain some heteroatoms or groups to satisfy the valence of the carbon, the fibrila-, they also have super defect sites. -f i > The most common atoms fixed on the surface carbons of fibrils are hydrogen, the predominant gas component during manufacture, oxygen due to its high reactivity, which are basically the edge carbons and contain heteroatoms or groups. and because it is very difficult to avoid traces of the element, and water, which is present at the first time due to the catalyst, pyrolysis to a turbine in a deoxygenated vacuum in the surface of a complex reaction with unknown mechanisms, but This product is known as CO and C02, in a 2 1 -project. The resulting fibril surface contains radicals in a C1-C4 alignment that are highly reactive with activated olefmas.The surface is stable in vacuum or in the presence of an inert gas, but maintains its reactivity until it is exposed to a reaction gas, therefore, the fibrils can be picolized at a temperature of Properly IOOO'C in a vacuum or in an inert atmosphere, cooled under these conditions and with a suitable molecule at all times. to your * lower for p i oror > ar un giupo fune luna! stable. Typical examples are: 1000"CF? Br-? La-0 - - - - - Fibrila Reac iva Surface (RFS) - + - 2 CO -r C02 followed by;? Or ßp RFS + CH2 - CHCOX - - Fi br 11 aP * -COX X = -0H, -Cl, - NH2, -H PF Anhydride l co - - - - - * > Fábr-ila-P '(COOH) 2 PFS + Cyan? Geno - - - - - - Fibpla-CN RFS + CH2 ^ -CH-CH2X - - - - - - Fibr il -P * CH2X X - ^ - H ?, -OU, -Ha 1 '- eno, PFS + H20 - - - - - F? Br? La = 0 í um. tide]) PFS + CH2 = CHCH0 - - - - - Fib i 1 -P 'CHO (ldeh id ico) PFS + CH2 = CH-CN - - - - - Fibrila-R'CN where R' is a radical radical buro (alkyl, cycloalkyl, etc.) * AXLE 2 Piecing of fibrils by one or two by the reaction of acrylic acid with super fi cial => fibrils free of. gram of fibrils BN in a porcelain container is used in a 2.54 c horizontal tube equipped with a mop.i and located in a h > .. tube of Lindberg tube. tremo => e.? ln equipped with "u / in / out of g < s. The tub. e? _ii? j c.ui't argon s cn, deso, igenada diuan'e] ñ The temperature of the furnace rises to 30 ß0 and is maintained for 30 minutes, after which, under a continuous flow of argon, the temperature rises in two hours. C up to 1000ßC, and it stays there for 16 hours »At the end of this time, the tube is cooled to a temperature of Environment (PT) under argon flow. The argon fines are then diverted to pass through a multi-neck ranch containing pure acrylic purified at 50 ° C and equipped with 1 gas inlet / s. The flow ... j .1.1 a c r f 1 i • - o '' »ap? »R n the a t * g n p! '• > s J gue I pji n i I 11 ¡- ambi t .Jnraute or not. > _. = > . A] Term of this year, - = > and I HI, H l, e e] i .. j.11 30 * 1 ll '' I re-,) i Ji i j 1 -, | n? > í-j? L I P, r 1 r H i nte i.ii i purge with ar gón, _¡. d > - -.n ^ -. by means of d i n ^ e. -I went to a tem eratu a) 0, C and an empty one, infe, jr.i to 12.7 c. Fl content in "" gone carboxyl ico se ueJ et? N-? I had an e. that of NaOH O. lOOfJ j. r et i Iulac J u with HCl 0.1 0 ha -at a final unit at a pH d i or ETE? FI? -. Fr a aci u of f ibrilas f une i ona 1 i '' da ^ by means of the reaction of a n j a t, t J a ico with super f i le-, de f ibri ementa, de o. J do The p ri l e. (Or eru ci and repeat m-t ite a simi l r 3] 5 p 1.) i. ed 1 m J enti t antepn ', e- ce' lo u] a pi isolis and the eti ti ti ti 3 carried out in a v- * > ío cié I / O_ < "Í _ 0 Ton. Steam is made up of se 'r se se se se se se se se se se se se se se se se se se se Va Va Va Va a a a a a a a a a a a a a a a. on 1 i: das by the reaction of a > id imlfi ü with fibril surfaces exempted from x 1 o The procedure is repeated as in example 2, except that the? i? v at room temperature is purified maleic anhydride (MAN) that is fed to the reactor by passing gas; argóri through a MAN bath in fusion at 80 * C. EXAMPLE 5 Preparation of fibrils -functional fibroblasts by reaction of acryloyl chloride with free-dried fibril surfaces The procedure is repeated as in Example 2, except that the reagent at room temperature is polyacrylated acylchloride, which is fed to the reactor by passing argon over pure acryloyl chloride at 25 ° C. The acid chloride content is determined by reaction with an excess of 0.100N NaOH and re-titration with 0.100N HCl. the pyrolysis of fibrils in vacuum deoxygenates the surface of the fibrils. In a TGA apparatus, pyrolysis at l 0ßC either in vacuum or in a flow of purified Ar provides an average weight loss of 3 * 4 for 3 samples of BN fibrils. Chromatographic evaluations of gases detected only CO and C02, in a ratio of approximately 2 liters, respectively. The resulting surface is highly reactive and activated olefins such as acrylic acid, acryloyl chloride, acri lamide, acrolein, maleic anhydride, allyl amine, allyl alcohol, or halide halides react at room temperature to form a product. > clean coughs that contain only this linked functionality on activated alephine. Accordingly, surfaces containing only carboxylic acids are obtained by reaction with acrylic acid or maleic anhydride; c-biene supe fit í containing only acid chloride by reaction with acryloyl chloride; surfaces are obtained which contain only aldehyde by reaction with arrolema; Are hydroxyl-only surfaces obtained from reaction with allyl alcohol? surfaces containing only amine are obtained from reaction with amine of aillo, and surfaces which only contain halide are obtained from reaction with allyl halide. 3. METALIZATION Background art is provided in March, A vdítced Organic Chemistry, 3"i'j. Ee ic, page 545. The aromatic CHs can be metallized with vario- .- organometallic reagents to produce carbon-metal bonds (CM), M is usually Li, Be, Mg, Al, or TI 5 however, other metals can also be used.The simplest reaction is a direct displacement. of hydrogen in activated aromatics: 1. Fibr ila-H + PL i - - - - - - Fibrila-Li + RH the reaction may require addition of a strong base, such as potassium t-butoxide or amines of chelation Afrotics solvents are necessary paraffin, benzene) 2. Fibpla-H + A1P3 - - Fibrila-A1R2 + RH 3. Firila-H + TI (TFA) 3 - - -> Fibrila-Tl (TFA) 2 + HTFA TFA = trifluoroacetate HTFA = t r i f luoroacetic acid Metalated derivatives are examples of primary functionally raised fibrils. However, they can react additionally to give other primary functionally unique fibrils. Some reactions can be carried out sequentially in the same apparatus without isolation of intermediates. 4. Fibrila-M + 02 _ - _ Fibpla-OH + MO M = Li, Al H + Fibpla-M + S - - - - - - Fibpla-SH • + • M + Fibpla-M + X2 - - - - - Fibpla-X + MX X = Halogen catalizador Fibpla-M + CH30NH2.HC1 - - - - - - Fibpla-NH2 + M0CH3 ether ea ta ta i iador Fibrila-Tl (TFA) 2 + NaOH - - - - - - Fibrila -OH tasting! Iced Fibpla-Tl (TFA) 2 - NH30H - - - - -, Fibr? la-NH2 + HTFA Fibpla-Tl (TFA) 2 + aq. CN - - - Fibr a-CN + TITEA + \ TFA Fibpla-CN + H2 - - - -. Fibri la-CH2-NH2 EXAMPLE 6 Preparation of fibrila-Li Urt gram of CC fibrils is placed in a porcelain vessel and inserted into a 2.54 quart quart tube reactor in a Lindberg tube furnace. The tube ends are equipped with gas inlet / outlet. Under continuous flow of H2, the fibrils are heated at 700 ° C for 2 hours to convert any surface oxygenate into C-H bonds. The reactor was then cooled to room temperature under H2 flow. The hydrogenated fibrils are transferred with dry, dehydrogenated heptane (with LY1H4) to a 1 liter, multi-necked round bottom flask equipped with a purified argon purge system to remove all air and matert an inert atmosphere, a conden- , a magnetic stirrer and a bule septum through which liquid can be added by means of a syringe. Under an argon atmosphere, a 2 * 4 solution containing 5 butyl lithium is added via syringe and the paste is shaken under gentle reflux for 4 hours. At the end of this period, the fibrils are separated by gravity filtration in an argon atmosphere glove and washed several times on the filter with heptane de-so. igenado, dry. The fibrils are transferred to a 50 c round bottom flask equipped with a stopper and dried under a vacuum of 1 / 10,000 tsrr at 50 * C. The lithium concentration is determined by the reaction of a sample of fibrils with excess O.IOON HCl in deionized water and re-titration with O.IOON NaOH to a final point with pH 5.0. EXAMPLE 7 Preparation of fibrila-Tl (TFA12 One gram of CC fibrils is hydrogenated as in example 5 and loaded into the multi-neck flask with HTFA that has been degassed by repeated purging with dry argon. of 5 mmol of TI (TFA) 3 in HTFA is added to the flask through the rubber septum and the paste is shaken under gentle reflux for 6 hours After the reaction the fibrils are collected which are dried as in example 1. EXAMPLE 8 Preparation of fibrila-OH (oxygenated derivative containing only functional OH-ionization) Half gram of lithiated fibrils prepared in Example 6 are transferred with undigested heptane, dried in a glove bag of alcohol atmosphere to a neck flask single 50 c equipped with a cap and magnetic stir bar The bottle is removed from the glove bag and shaken on a magnetic stirrer The plug is *, 33 then open to the air and the paste is stirred for 24 hours. At the end of this time, the fibrils are separated by filtration and washed with aqueous MeOH, dried at 50 ° C and under a vacuum of 12.7 cm. The concentration of OH groups is determined by reaction with a standardized solution of acetic anhydride in dioxide (0.252 M) at 80 ° C to convert the OH groups into acetate esters, and in this way, release 1 equivalent of acetic acid / mol of reacted anhydride. The amount of total acid, free acetic acid and unreacted acetic anhydride is determined by titration with NaOH O.IOON to a final point at a pH of 7.5. EXAMPLE 9 Preparation of Fibila-NH2 A gram of felled fibrils is prepared as in Example 7. The fibrils are pulped in dioxane and 0.5 g of dihydroxyphosphine is added in dioxane. The paste is stirred at 50 ° C. for several minutes, followed by the addition at 50 ° C. of gaseous ammonia for 30 minutes. The fibrils are then separated by filtration, washed in diaxapo, then in deionized water and dried at 80 ° C. in a vacuum of 12.7 cm. The. Amine concentration is determined by reaction with an excess of acetic anhydride and a re-titration of free acetic acid and unreacted anhydride with NaOH O.IOON. 4. AROMATIC COMPOUNDS POLY UCLE REAS DERIVATIVES, COMPOUNDS ARROATIC POLYHETERONUCLEARS DERIVATIVES AND DERIVED FLAT MACROCYCLICAL COMPOUNDS The graffiti surfaces of fibrils allow the physical adsorption of aromatic compounds. The attraction is realized through the van der Waals forces. These forces are considerable between multiple-ring heteranuclear aromatic compounds and the carbons of the basal plane of the graphite surfaces. Desorption can occur under conditions where competitive surface adsorption is possible or when the adsorbate has a high solubility. EXAMPLE 10 Adsorption of porphyrins and phthalocyanins in fibrils The preferred compounds for physical adsorption in fibrils are derived particles or phthalic derivatives known to be strongly adsorbed on graphite or carbon black. Several compounds are available, for example, a tetracarboxylic acid porphyrin, cobalt (II) phthalocyanine or di lithium phthalacyanine. The last two compounds can be derived in the form of carboxylic acid. The loading capacity of the porphyrin or of more phthalocyanines can be determined by decolorizing the solutions when they are added incrementally. The .7 dark colors of the solutions (dark pink for the porphyrin of tetracarboxylic acid in MeOH, dark blue-green in the case of Co (II) or of the phthalocyanine of dilithium in acetone or pyridine) are discharged according to the molecules they remove by adsorption on the black surface of the fibrils. The loading capacities were estimated by this method the traces of the derivatives were calculated from approximate suspensions (approximately 140 square Angstroms). For an average surface area of fibrils of 250 m2 / g, the maximum load will be approximately 0.3 mntol / g. The porphyrin of tetracarb acid i 1 ico was analyzed by titration. The integrity of the adsorption was tested by color release in aqueous systems at room temperature and at elevated temperatures. The fibril pastes were initially mixed (W ring mixer) and stirred during loading. Some of the pulps were subjected to ul trasonido after the suspension of the color discharge, but without effect. After loading, experiments 169-11, -12, -14 and -19-1 (see Table II) were washed in the same solvent to remove the occluded pigment. All provided a continuous weak ink in the wash effluent, such that it was difficult to determine the saturation point accurately.

Experiments 168-18, and - 19--2 used calculated amounts of pigments to load and were washed only very slightly after ca.ga. The porphyrin of tetracarboxylic acid (from acetone) and phthalocyanine Co (from pyridine) were loaded into fibrils for further characterization (experiments 169-18 and -19-2, respectively). Porphyrin analysis of tet racarboxylic acid The addition of excess base (pH 11-12) caused an immediate pink coloration of the titration paste. While this did not interfere with the figuration, it was shown that at a high pH level, the porphyrin exhibited desorption. The concentration of carboxylic acid was determined by re-titrating excess NaOH using pH 7.5 as the end point. The titration provided a load of 1.10 meq / g of acid, equivalent to. 75 meq / g of porf i r i na. Analysis of cobalt or phthalocyanine of dilithium The concentrations of these adsorbates were estimated from de-colouration experiments only. The point where the blue-green ink did not fade after -30 minutes was taken as the saturation point. Numerous polynuclear substituted aromatic compounds or ai-omát i > : -'-) pol and substituted heteronucleres were adsorbed on fibril surfaces. Par-to his adhesion, the? The aromatic rings must be greater than two per functional pendant ring, and therefore substituted, substituted, substituted phenothianes, etc., with three fused rings, or poly-functional derivatives with four or more. more fused rings can be used in place of the porphyrin or of the derivatives of phthalocytes, in the same way, heterocyclic substituted aromatics as for example quinolines, or romanic compounds several times substituted Those containing four or more rings may be used Table II presents the results of the loading experiments for the three derivatives of porf i rirta / f ta loe iani na TABLE II SUMMARY OF ADSORPTION EXPERIMENTS Example Addebate Experiment » Weight of Sun. No. Fib, g 1 A 169-11 TCAPorph 19.6 mg Acet 10B 169-12 TCAParph 33.3 g H20 1 C 169-14 DiLiPhth 119.0 mg Ace 10D 169-19-1 CoPhth 250.0 g Pir 10E 169-18 TCAPorph 1.00 g Acet 1 F 169-19-2 CoPhth 1.40 a Pi F.je plo C rga Ti tulac ion g / g form meq / g 10A 0.18 g / 9 acid has 10B 0.11 sl of Na na 10C 0.170 Li na 10D 0.187 Co 0.335 (cal) 10E 0.205 acc? ) 1 F 0.172 Co 0.303 (cal) TCAPsrph = porf i tetracarboxylic acid bead DiLiPhth = silicon phthalocyanine CoPhth = cobalt (II) allocianine (cal) = calculated (T) = i tulation 5. NITRIC ACID OXIDATION 0 CHLORATE The literature on the oxidation of graphite by strong oxidants such as, for example, potassium chlorate in concentrated sulfuric acid or in concentrated nitric acid, includes R.N. Smith, Gjuarterly Review 13, 287 (1959) j M.J.D. Low, Chem. Rev. 60, 267 (1960)), Generally, edge carbons (including defective sites) are attacked to provide mixtures of carboxylic acids, phenols, and oxygenated groups. The mechanism is complex and involves radical reactions. EXAMPLE 11 PREPARATION OF FUNCTIONAL FIBRILLS BY CARBOXY L ACID USING CHLORATE The sample of CC fibrils was formed into paste in concentrated H2SO4 by mixing with a spatula and then transferred to a "reactor" bottle equipped with an inlet / outlet. gas and an agitator on top.

Under agitation and with a slow flow of argon, the charge of NaC103 was added, in parts at room temperature during the period of the experiment. Chlorine vapors were generated throughout the course of the experiment which were removed from the reactor in a tranche of aqueous NaOH. At the end of the experiment, the fibril paste was emptied into ice chips and filtered in vacuum. The filter cake was then transferred to a Soxhlet thimble and washed in a Soxhlet extractor with deionized water, changing the clean water every several hours. The washing was carried out continuously until the fibril sample, when added to fresh deionized water, did not lose the pH of the water. The fibrils were then separated by filtration and dried at 100 ° C overnight under a 12.7 cm vacuum.

Carbohydric acid content was determined by reacting a sample with an excess of 0.100 N NaOH and re-titrating with O.lOOn HCl to a final point at a pH of 7.5. The results appear in the Table. TABLE III SUMMARY OF DIRECT OXIDATION EXPERIMENTS Rec Acid, Component, g Axis. Experiment Fibrils NaC103 c H2S04 No. : H A 168-30 10.0 8.68 450 1 1B 168-36 12.0 13.9 600 Spend time. hours pH of washing weight meq / g HA 24 5.7 10.0 0.78 11B 24 5.9 13.7 0.75 EXAMPLE 12 PREPARATION OF FUNCTIONAL FIBRILLS IZADAS BY ACID CARBOXSLICO USING NITRIC ACID A heavy sample of fibrils was formed into paste with nitric acid of the appropriate strength in a round-bottomed multi-necked toothed reactor bottle equipped with a shaker on top and a water condenser. Under constant agitation, the temperature was adjusted and the reaction was carried out for the specified time. Brown fumes were released shortly after the temperature exceeded 70 ° C, regardless of the strength of the acid. After the reaction, the paste was emptied in t-ice ice and diluted with deionized water. The paste was filtered and the excess acid removed by washing in a Saxhlet extractor, replacing the reserve with fresh deionized water every several hours, until the sample in paste form did not change the pH of the deionized water. The fibrils were dried at 100 ° C overnight in a 12.7 cm vacuum. A weighted portion of fibril was reacted with standard O.sub.100 N NaOH and the carboxylic acid content was determined by re-titration with 0.100 N HCl. The surface oxygen content was determined by XPS. The dispersion capacity in water was tested at 0.1% by weight by mixing in a Waring blender at high speed for two minutes. The results appear in Table 4. TABLE IV SUMMARY OF DIRECT OXIDATION EXPERIMENTS Components Di p Gms. c acid Temp. Ahem. Fibri acid concentrated ßC Time 12A i (BN) 300 70 * 4 RT 24 hr 12B KBN) 300 15 rflx 48 12C 20 (BN) 1.0 1 70 rflx 7 12D 48 (BN) 1.0 1 70 rflx 7 Disp loss meq / g ESCA, C to H2I Ejem. by weight COOH * 4 0 12A 0 < 0.1 98 2 P 12B 5 * 4 < 0.1 not analyzed P 12C 15 * 4 0.8 not ana 1 iced G 12D 20 * 4 0.9 not analized G P = limited; G = good 6. SECONDARY DERIVATIVES OF LIFTED FUNCTIONAL FIBRILLES Fibrils functionalized by carboxylic acid The number of secondary derivatives that can be prepared from only carboxylic acid is essentially unlimited. Alcohols and amines are easily linked with acid to provide stable esters or stable amides. If the alcohol or amine is part of a difunctional or functional psi molecule, then the link through 0- or NH- leaves the other functionalities as hanging groups. Typical examples of secondary reagents are: GENERAL FORMULA GROUP EXAMPLES PENDANT HO-P, P = alkyl, P-methanol, phenol, trifluoro-aralkyl, aryl, carbon, polyester with f-haloethanol, OH-termination, polymer silanols, SiR'3 H2N-R R = as R-amines, anilines, to inírß up fluorinated, silylamine * «polyamides with amine termination C1-SiR3 SiR3- c lorosi l nos HO-R-OH, Realkyl, HO- and i-glycol, PEG, penta-aralkyl, CH20-erythritol, bis-phenol A H2N-R-NH2, H2N- eti lendiamine, polyethyl-R = aralkyl alkyl endiami X-R-Y, R = alkyl, Y-polyamine amides, etc? X = OH or NH2? mercaptoet nol Y = SH, CN, C = 0, CHO, alkene, aromatic, heterocycles The reactions can be carried out using any of the methods developed to esterify or amines carboxylic acids with alcohols or amines. Among these, the methods of H.A. Staab, Angew, Chem. Internat, Etit., (1), 351 (1962) using N, N'-carboni ldi imidazole (CDI) as an acylating agent for esters or amides, and of G.W. • Ire Anderson, et al., J. Amer. Chem. Soc. 86, Í839 (1964), using N-hydroxysuccinimide (NHS) to activate carboxylic acids for amidation. EXAMPLE 13 PREPARATION OF SECONDARY DERIVATIVES OF FIBRILLES FUNCTIONALIZED N, N'-carboni ldi imidazole Aprotic, dry, clean solvents (eg, toluene or dioxide) are required for this procedure. Stoichiometric quantities of reagents are sufficient. For steres, the carboxylic acid compound reacts in an inert atmosphere (argon) in toluene with a stoichiometric amount of CDI dissolved in toluene at room temperature for two hours. During this time, C02 is issued. After 2 hours, alcohol is added together with catalytic amounts of Na-ethoxide and the reaction proceeds to BO'C for 4 hours. In the case of normal alcohols, the yields are quantitative. The reactions are: 1. R-C00H + Im-Co-Im > R-CO-Im + HIm + HIm + C02, Im = Imidazole gone, HIm = Imidazole NaOEt 2. R-CO-Im - + R'OH > R-C0-0R '+ HIm The amidation of the amines occurs in a non-catalyzed manner at room temperature. -The first step in the procedure is the same. After the emission of C02, a stoichiometric amount of amine is added at room temperature and the reaction is carried out for 1-2 hours. The reaction is quantitative. The reaction is: 3. R-CO-Im + R'BG2 > R-CO-NHR + HIm N-hydroxy isuccini ida The activation of carboxylic acids for primary amino-amine amines occurs through the M-hydroxysuccinamine ester; Carbonate is used to bind the released water as a substituted urea. The NHS ester is then converted to room temperature in the amide by reaction with primary amine. The reactions are: 1. R-COOH + NHS + CDI > R-CONHS + substituted urea 2. R-CONHS + R'NH2 r- > R-CO-NHR 'SILILATION Trialquilsi 1 i Ichlorides or trialkylsilanols react immediately with H acid in accordance with: R-COOH + Cl-Si' 3 > R-CO-SiR'3 + HCl Small amounts of Diaza-1, 1, 1, -bicyclooctane (DABCO) are used as catalysts. Suitable solvents are dioxane and toluene. EXAMPLE 14 PREPARATION OF ESTER / ALCOHOL DERIVATIVES FROM FIBRILLES FUNCTIONALIZED WITH CARBONOXY ACID Fibrils functionalized with carboxylic acid were prepared as in example 11. The carboxylic acid content was 0.75 meq / g. The fibrils reacted with a stoichiometric amount of CDI in an inert atmosphere with toluene as solvent at room temperature until the CO 2 emission was suspended. Thereafter, the pulp reacted at 80 ° C with a 10-fold molar excess of polyethylene glycol (molecular weight 600) and a small amount of NaOEt as a catalyst. After two hours of reaction, the fibrils were separated by filtration, washed with toluene and dried at 100 * C. EXAMPLE 15 PREPARATION OF AMID / AMINE DERIVATIVES FROM FIBRILLES FUNCTIONAL LIFTED WITH CARBOXYLIC ACID (177-041-1) 0.242 g of oxidized fibrils were suspended with chlorate (0.62 meq / g) in 20 ml of anhydrous dioxide under agitation in a 100 ml round bottom flask equipped with a stopper of serum. A 20-fold molar excess of N-hydroxysuccinimide (0.299 g) was added and allowed to dissolve. This was followed by the addition of a 20-fold molar excess of 1-et i 1-3- (3-dimet i laminoprop i 1) -carbodi ida (EDAC) (0.510 g) and the stirring continued for 2 hours at room temperature. ambient. At the end of this period the application was suspended, and the supernatant was aspirated and the solids were washed with anhydrous dioxane and MeOH and filtered on the polysulphone membrane of 0.45 microns. The solids were washed with additional MeOH on the filter membrane and dried in vacuum until no further weight reduction was observed. The yield of the oxidized fibrils activated with NHS was 100 * 4 based on the weight gain of 6 * 4 observed. 100 μl of ethendiamine (en) was added to 10 ml of NaH003.2 M regulator. An equivalent volume of acetic acid (HOAc) was added to maintain the pH around 8. Oxidized fibrils activated with NHS were added (0.310 g) under vigorous stirring and a reaction was carried out for 1 hour. An additional 300 μl of et i lendiamine and 300 μl of HOac were added for an additional 10 minutes. The solution was filtered on a 0.45 micron polysulfone membrane and selectively washed with NaHCO3 buffer, 1 * 4 HCl, deionized water and EtOH. The solids were dried under vacuum overnight. The HCl salt was converted back to the free amine by reaction with NaOH (177-046-1) for further analysis and reactions. ESCA was carried out to quantify the amount of N present in the aminated fibrils (GF / NH2). The ESCA analysis of 177-046-1 showed 0.90 to * 4 N (177-059). To additionally evaluate how much of this N is present in both reactive and reactive amine groups, a derivative was made by reaction in gas phase with pentaf luorobenzaldehyde to produce the corresponding Schiff base bonds with the available primary amine groups. The ESCA analysis still showed 0.91 at * 4 N, as expected, and 1.68 at * 4F. This is traduced in 0.34 at * 4 of N present as reactive primary amine in the aminated fibrils (5 F per molecule of pentaflurobenzaldehyde). It is expected that a level of 0.45 at'4 N assumes a complete reaction with the free ends of each N. The observed level indicates a very high yield from the reaction of N with fibrils acitvated with NHS and confirms the reactivity of the groups of free amines available. At the level of 0.34 at * 4 N present as free amine calculated from the ESCA data, there would be an almost complete coverage of the fibrils by the free amine groups allowing the coupling of other materials. EXAMPLE 16 PREPARATION OF SIL ILO DERIVATIVE APART FROM FUNCTIONALIZED FIBRILS BY CARBON ACID Organic acidic prepared fibrils prepared as in example 11 were formed in diaxana paste in an inert atmosphere. Under stirring, a stoichiometric amount of chloratinyllysilane was added and a reaction was carried out for 0.5 hours, after which several drops of a 5 * 4 solution of DABCO in dioxane were added. The system reacted for an additional hour, after which the fibrils were collected by filtration and washed in dioxane. The fibrils were dried at 100 * in a vacuum of 12.7 c during the night. Table 5 summarizes the preparations of secondary derivatives. The products were analyzed by ESCA i to determine the surface contents of C, O, N, Si and F. TABLE V SUMMARY OF SECONDARY DERIVATIVE PREPARATIONS Reagent Hanging group ESCA analysis, * 4 ATOM SCN 0 If F co or grew - 98.5 - 1.5 - oxidized by -COOH, C = 0, C-OH 92.4 - 7.6 - chlorate H2N-C2H4-NH2 -C0NHC2H4NH2 - 99.10 0.90 - - -C0NHC2H4N = 0C6F5 - 97.41 0.91 - - 1.68 EXAMPLE 17 PREPARATION OF SILYLIDE DERIVATIVE A START OF FUNCTIONAL FIBRSAS IZADAS BY. CARBOXYLIC ACID Functional fibrils i. The acid-based preparations prepared as in Example 11 are pulped in dioxane in an inert atmosphere. Under stirring, a stoichiometric amount of chlorotrifelium is added, and a reaction is carried out for 0.05 hours, after which several drops of a 5 * 4 solution of DABCO in dioxane are added. The system reacts for an additional hour, after which the fibrils are collected by filtration and washed in dioxane. The fibrils are dried at 100 ° C overnight in a 12.7 cm vacuum. Table VI summarizes the secondary derivative preparations.

The products are analyzed by ESCA. The analysis confirms the incorporation of the desired hanging groups. The products are analyzed by ESCA to determine the surface contents of C, 0, N, Si and F. TABLE VI Summary of secondary derivative preparations ANALYSIS ESCA * 4 REAGENT ATOM GROUP HANGING S. CNO Si F CH3CH20H -C00CH2CF3 NOT ANALYZED PolyEG-600 -CO- (0C2H4O-) H NON-ANALYZED H0-C2H4-SH -C00C2H4SH Cl-SiEt3 -C0SiEt3 Fibrilas works with sulfonic acid Aric acid isic acids, in accordance with that prepared in example 1, can be further reacted to provide secondary derivatives. Sulfonic acids can be reduced to mercaptans by LIA1H4 or the combination of tri-phenylphosphine and iodine (March, J.P., page 1107). They can also be converted to sulfonate esters by reaction with dialkyl ethers, i.e., Fibrila-S03H + R-Qr-R > Fibrila-S020R + ROH Fibrils are activated by electrophysiological addition to oxygen-free fibril surfaces or by metalization The primary products that can be obtained by the addition of activated electrophiles to oxygen-free fibril surfaces have - COOH, -COCÍ, -CN, -CH2NH2, CH2CH, -CH2- halogen, or HC = 0 pendants. These can be converted into secondary derivatives as follows: Fibrila-COOH - - - - - > watch up. Fibrila-COCl (acid chloride) + HO-R-Y - - - > F-COO-R-Y (Sections 4/5) Fibrila-COCl + NH2-R-Y > F-CONH-R-Y Fibrila-CN + H2 > F-CH2-NH2 Fibrila-CH2NH2 + HOOC-R-Y > F-CH2NHC0-R-Y Fibrila-CH2NH2 + 0 = CR- 'Y > F-CH2N = CR-R * -A and Fibrila-CH20H + 0 (C0R-Y) 2 > F-CH20C0R-Y Fibrila-CH20H + HOOC-R-Y > F-CH20C0R-Y Fibril-CH2-halogen + Y "> F-CH2-Y • + X" Y "" = NC0 ~, -OR "Fibril-C = 0 + H2N-RY> FC = NRY Fibrill function lized by adsorption of polynuclear aromatic compounds or polyheteronuclear or flat macrocycles, Ftaloe iani. na di di tio: Ert general terms, the two Li + ions are displaced from the phthalocyanine group (Pe) for most metal complexes (particularly the lens). Accordingly, the displacement of the Li + ions with a metal ion bound with non-labile ligands is a method for placing stable functional groups on the surfaces of fibrils. Almost all transition metal complexes displace Li + from Pe to form a stable, non-labile chelate. The point here is therefore to couple this metal with a suitable ligand, cobalt phthalocyanine < II) The cobalt (II) complexes are especially suitable for this. The Co ++ ion can be substituted by the two Li + ions to form a very stable chelate. The Co ++ ion can then be coordinated with urt ligand such as for example nicotinic acid, which contains a pyridine ring with a pendant carboxylic acid group and which is known to be preferably linked to the pyridine group. In the presence of excess nicotine acid, Co (II) Fe can be electrochemically oxidized in Co (III) Pe, forming a non-labile complex with the pyridine portion of nicotinic acid. Accordingly, the free carboxylic acid group of the nicotinic acid ligand is firmly fixed on the fibril surface. Other suitable ligands are aminopyridines or eti lendia inas (pendant NH2), ercaptopi ridine (SH), or other polypunctional ligands containing either an amino moiety or a pyridyl moiety at one end, and any desirable function in the other. 7. THREE-DIMENSIONAL STRUCTURES Oxidized fibrils are more easily dispersed in aqueous media than non-oxidized fibrils. Stable, porous, ridiculous structures with mesopors and macropores (pores of more than 2 nm) are very useful as catalysts or chromatography supports. Since the fibrils can be dispersed on an individualized basis, a well dispersed sample stabilized by crosslinks allows the construction of such support. Functional fibrils are ideal for this application since they can easily be dispersed in aqueous or polar media and the functionality provides crosslinking points. Additionally, the functionality provides points to support the catalytic points or cram tográf icos. The final result is a rigid, three-dimensional structure with its accessible total surface area with functional sites where the active agent can be carried. Typical applications for these supports in catalysis include their use as a highly porous support for metal catalysts placed by impregnation, for example precious metal hydrogenation catalysts. In addition, the ability to anchor molecular catalysts by means of bonding on the support through the functionality combined with the very high porosity of the structure makes it possible to carry out homogeneous reactions in a heterogeneous manner. The bound molecular catalyst is essentially suspended in the continuous liquid phase, similar to a homogeneous reactor, where the advantages of selectivities and velocities that accompany the homogeneous reactions can be used. However, since it is attached to the solid support this allows easy separation and recovery of the active catalyst and in many cases very expensive. These rigid, stable structures also make it possible to carry out reactions that were previously very difficult, such as for example asymmetric synthesis or affinity chromatography by fixing a suitable enantiomeric catalyst or selective substrate on the support. Derivation through metallo-Pe or metallo-porphyrin complexes also allows the recovery of the bound metal ligand, and in addition, of any molecule bound to the ligand through the secondary derivatives. For example, in the case in which the three-dimensional structure of fibrified func- tions is an electrode, or part of an electrode, and the functionalization resulted from the adsorption of Co (II) Pe, the electrochemical oxidation of Co ( II) in Co (III) in the presence of nicotinic acid will produce a Co (III) -pyridyl non-labile complex with a carboxylic acid as a pendant group. The attachment of an appropriate arttigene, antibody, catalytic antibody, or other suitable site-specific entrapment agent will allow selective separations of molecules (affinity chromate raffia) that are otherwise very difficult to achieve. After washing the electrode to remove the occluded material, the Co (II) complex containing the target molecule can be electrochemically reduced to recover the labile Ca (II) complex. The ligand in Co (II) containing the target molecule can then be recovered by mass-action substitution of the labile Ca (II) ligand, thus effecting a separation and recovery of molecules that are otherwise very difficult or costly to carry out (for example, chiral drugs). Another example of three-dimensional structures are fibril-ceramic composites. EXAMPLE 18 Preparation of alumina-fibril compounds (185-02-01) One gram of fibrils oxidized by nitric acid (185-01-02) was highly dispersed in 100 cc of deionized water using a U / S disintegrator. The fibril paste was heated to 90 ° C and a solution of 0.04 mol of aluminum tributhoxide dissolved in 20 g of propanol was slowly added. The reflux continued for 4 hours, after which the condenser was removed to remove the alcohol. After 30 minutes the condenser was returned and the pasta subjected to reflux at 100 ° C overnight. A black colloidal solution with a uniform appearance was obtained. The colloidal solution was cooled to room temperature and after one week, a black gel with a smooth surface was formed. The gel was heated at 500 ° C in the air for 12 hours. The alumina-fibril compounds were examined by SEM. Micrographs of cracked surfaces showed a homogeneous dispersion of the fibrils in the gel. EXAMPLE 19 Preparation of silica-fibril compounds (173-85-03) Two grams of fibrils oxidized by nitric acid (173-83-03) were highly dispersed in 200 g of ethanol using ul trasoni fica. A solution of 0.01 mol of tetraethoxysilane dissolved in 50 ce of ethanol was slowly added to the paste at room temperature, followed by 3 cc of concentrated HCl. The mixture was heated to 85 ° C and maintained at this temperature until the volume was reduced to 100 ° C. The mixture was cooled and stored until a solid black gel formed. The gel was heated at 300 ° C to the air. The ice-fibril compound itself was examined by SEM. The micrographs of the cracked surfaces showed a homogeneous dispersion of the fibrils in the gel. Similar preparations with other ceramics, such as zirconia, titania, rare earth oxides as well. as ternary oxides can be prepared.

As illustrated in the description and previous examples, the invention has application in the formulation of a wide variety of funneled nanotubes. The terms and expressions that have been used are used as terms of description and are not intended to limit the invention, and there is no intent in the use of such terms or expressions to exclude any equivalent of the features shown and described as parts of the invention. the same, recognizing that various modifications are possible within the scope of the invention.

Claims (11)

CLAIMS l. A composition of the formula Ta matter < CnHL-H = tm where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic nanotube having a ratio between length and diameter greater than 5 and a diameter smaller than 0.5 μ, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide , COSH, SH, COOR ', SR', SiR'3, YES -0R '- yR' 3-y, Si4-0-SiR'2 * - 0R ', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, P. 'is alkyl, aryl, cycloalkyl, aralkyl, or cycloalkyl, R "is falloalkyl, fluoroaryl, fluorocycloalkyl, or well, it is a halide, and 7. is a carboxylate or tri-fluorouracetate. 2. A composition of the matter of the formula (CnHL-H =? M where the atoms of erarbono, Cn, are superficial carbons of a graphitic fibril, substantially cylindrical substantially free of pyrolitically deposited carbon, a projection of the layers of graphite over said fibrils extends at a distance of at least 2 diameters of fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP.', SiR'3, Si-Í-OR '? -yR' 3-y, Si - (- 0-SiR '2-> - OR', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or cycloalkyl, R "is a haloalkyl, fluaroaryl, f luorocloalkyllo, or f 1uoroa at 1 qui 1o, X is a haluera, and Z is a carboxylate or tri f luoroacetats 3. A composition of the material in accordance with that claimed in rei indication 2 wherein said fibril comprises cylindrical graphitic sheets whose axes c are substantially perpendicular to its cylindrical axis 4. A composition of the material according to claim 2, wherein the external diameter of said fibrils is inferior at 0.1 μ 5. A composition of the material of the formula (CnHL P. where the carbon atoms, Cn, are surface atoms of a fishbone fibril, n is an integer, L is a nelemer less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', SiR'3, Si-Í-OR '-? - and R' 3-y, Si-t-0-SiR'2 - OR ', R ", Li, ALR'2 , Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or else aryl-aryl, P-effluoroalkyl, fluoroaryl, haloalkyl, A good fluoroara Iqui lo, X is a halide, and Z is a carboxylate or trifluoroacetate. 6. A composition of the material of the formula (CnHL-Mm where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic nanotube having a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOP ', SP.', Si.R'3, Si-fr-OR '-) - yR' 3-y, Si - (- 0-SiR ' 2- > ^ OP ', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R' is selected from the group consisting of alkyl, aryl, cycloalkyl , to ralquilo, cieloa rilo, R "is f luaraa lqu. I, fluoroaryl, fluorine, or fluoroalkyl, X is a hetero, and Z is a carboxylate or tri-fluoroacetate, and conditions other than when each R is an oxygen-containing group, COOH is not present. 7. A composition of the matter of the formula (CnHL * -Rm where the atoms of cartiono, Crt, are superficial carbons of a graphitic fibril, its tanc ially cylindrical, substantially free of carbon deposited p rolically, the projection of the graphite layers on said fibrils extends at a distance of at least 2 diameters of fibril n an integer, L is a child less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP.', SiR'3, YES + -0R '- »yR' 3-y, Si - (- 0-SiR '2- > ~ OR', R", Li, ALR '2, Hg-X, T1Z2 and Mg-X, and is an integer equal to, or less than 3, R' is ic'uils, aryl, cycloalkyl, aralkyl, or ciel aa ri lo, R "is fl What is fluoroaryl, what is it? What is it? What is it? What is it? What is it? What is X? What is X? A is a halide, and Z is a carboxylate or a tif-luoacetate, and also conditions that when each of R is a group that contains oxygen, COOH is not present 8. A composition of the material as claimed in claim 7, wherein said fibril comprises cylindrical graphite sheets whose axes c are substantially perpendicular to its cylindrical axis. Matter of conformity with that claimed in rei indication 7, where the external diameter of said fibrils is less than 0.1 μ 10. A composition of the matter of the formula (CrsHL Rm where the carbon atoms, Cn, are sup erficials of a fishbone fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same, and is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halu.ro, COSH, SH, COOR ', SR', SiP. '3, YES.4-0R' -i-yR '3-y-, Si-í-0-SiR * 2 * - OP', R ", Li., Al.R'2, Hg-X, T1Z2 and Mg-X, and is an integer igeeal or less than 3, R 'is alkyl, aryl, cycloalkyl, alkylo, or cycloalkyl, P "is haloalkyl, fluoroaryl, haloalkyl fluorine, or good f luoroaralqu. i lo, X is a halide, and Z is a carboxylate or tr i f luoroacetate, and further conditions that when each R is an oxygen-containing group, COOH is not present. 11. A composition of the subject of the formula < CnHL * Rm where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic nanotube having a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, n is an integer, L is a number less than O.ln and m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP', SiR'3, Si - * - 0R '- »and R' 3-, Si- -O-SiR '2 * -OR', R", Li, ALR'2, Hg-X , T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, cycloalkyl, R "is f luoroa Iqui lo, fluoroarilo, f luoroc icaloalqui lo, or f luoro ralqu i lo, X is a halide, and Z is a carboxylate or t ri f luoroaceta to, and also conditions that each of R does not contain oxygen. 12. A composition of the material of the formula (CnHL R where the carbon atoms, Cn, are surface carbons of a substantially cylindrical, graphitic fibril, substantially free of carbon deposited p rolically, the projection of the graphite layers in said fibrils extends to dinner distance of at least two diameters of fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and selects within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', SiR'3, Si-Í-OR '? And R' 3-y, Si-í-0-SiR '2? - 0P.', R ", Li, ALR'2 , Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or elsealpharyl, R "is falloalkyl, f lu. To oroar i lo, f luoroc icloa Iqui lo, or f luoroa ralqu i lo, X is a halide, Z is a carboxylate or tri f luoroacetate, and also conditions that each of R does not contain oxygen, 13. A composition of the material claimed in claim 12, wherein said fibril comprises cylindrical graphitic sheets whose axes c are substantially perpendicular to its cylindrical axis. 14, A composition of the subject matter claimed in claim 12, wherein the external diameter of said fibrils is less than 0.1 μ. 15. A composition of the matter of the formula (CnHL-Hm where carbon atoms, Cn, are surface atoms of a fishbone fibril, n is an integer, L is a number less than O.ln m is a number less than 0.5n, each of P is the same is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halu.ro, COSH, SH, COOR ', SP. ', Yep. '3, Si - OR' -) - yR '3-y, Si-É-O-SiR' 2- > - OP. ', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R' is alkyl, aryl, ie, aralkyl, or else i, R "is f luoroalkyl, fluoroaryl, f luoroc iclo I, lo or f luoroa r lqu i lo, X is a h lu.ro, Z is a carboxylate or tri-fluoroacetate, and furthermore that each P does not contain oxygen. 16. A composition of the material of the formula (CnHL-Rm where the carbon atoms, Cn, san superficial carbons of a graphitic nanotube, substantially cylindrical having a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, each of A is selected from 0 0 0 0 I I I I 0Y, NHY, C-0Y, C-NR'Y, C-SY, C-Y, -CR'2-0Y, N-Y, and C-Y, And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen or an enzyme substrate, an enzyme inhibitor or a transition state analogue of a protein. enzyme substrate is either selected from R ', -OH, R'-NH2, R'SH, R'CHO, R'CN, R'X, R'SiR'3, R'Si40R' -) - and R ' 3-y, R 'Si + O-SiP. '2-H3R', R'-R ", R'-N-CO, (C2H40rt.H, 4C3H60 e-jH, 4C2H40) wr ', (C3H60) wR' and R ', and is an equal integer, or less than 3, R * is alkyl, aryl, cycloalkyl, radical, or cycloaryl, R "is f-haloalkyl, fluoroaryl, f lo-loquel, or f erally alkaline, X e- = > a halide, and 7 is a car-box i 1 a t or t ien t r i f luoroaceta to, u > is a whole number greater than 1 and less than 200. 17. A composition of the formula mnin (CnHL * Pm where the carbon atoms, Cn, are surface carbons of a substantially cylindrical, graphitic fibril substantially free of carbon deposited pi rolically, the projection of the graphite layers in said fibrils extends over a distance of at least two diameters of fibril, n is an integer, L is a number less than O.ln, m is a lower number at 0.5n, each of A is selected from 0 0 0 0 I I I I 0Y, NHY, C-0Y, C-NR'Y, C-SY, C-Y, -CR'2-0Y, N-Y, and C-Y, And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, a nucleotide, an antigen or an enzyme substrate, enzyme inhibitor or the transition state analogue of a protein. enzyme substrate is either selected from P ', -OH, R'-NH2, P'SH, R'CHO, P'CN, P'X, R'SiR'3, R'Si-ÍOR' + and R ' 3-y, P 'Si4-0-SiR' 2-H3P ', P'-P ", R'-N-CO, (C2H40-H-IH, 4C3H60 e-? H, 4C2H40) en-r', (C3H60) ei / ~ R 'and P', and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or ci. C 1 or ryl, R "is f luoroalqui lo, fluoroarils, f luoroc iclaalqui lo, or f luoroa ra Iqu. i, X is a halide, Z is a carboxylate or tri-f luoroacetate, and w is a whole number greater than 1 and less than 200. 18. A composition of the material claimed in claim 17, wherein said fibril comprises cylindrical graphite sheets whose c-axes are spatially perpendicular to their cylindrical axis. 19. A composition of the subject claimed in claim 17, wherein the external diameter of said fibrils is less than about 0.1. μ. 20. A composition of the matter of the formula (CnHL Am where the carbon atoms, Cn, are surface atoms of a fishbone fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of A is selected from 0 0 0 0 II.I 0Y, NHY, C-0Y, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, and CY, Y is an appropriate functional group of a protein, a peptide, an enzyme, an anticejerpo, a nucleotide, an oligonucleotide, an antigen or an enzyme substrate, enzyme inhibitor or the analog of the transition of an enzyme substrate or is selected from P ', -OH, P'-NH2, P'SH, R'CHO, R'CN, R'X, R'SiR'3, P'Si- (0P '* yP'3-y, R' Si40-SiR '2- 3R', P'-P ", R'-N-CO, (C2H40- »wH, 4C3H60 * wH, 4C2H40) > -i-r ', (C3H60) wR' and R ', and is an integer equal to or less than 3, P' is alkyl, aryl, cycloalkyl, aralkyl, or cyclic, P "is fl uoroalk i lo, fluoraaplo, f luoroe i cloalqui lo, or f 1uoraa ra 1 qu i 1, X is a h luro, 7 is a car box or tr if luaroaceta to, and w is a number upper integer 1 and less than 200. 21. A composition of the matter of the formula (CnHL (R'-R) m where the carbon atoms, Cn, are surface atoms of a graphitic, substantially cylindrical nanotube that has a ratio between length and diameter greater than 5 and urt diameter less than 0.5 μ, n is an integer, L is a number less than O.ln, is a number less than 0.5n, each of P is the same and it is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COCP ', SR', SiR'3, SÍ4-0R '- »R' 3-y, SÍ4-0-SÍR '2? - OR', R", Li, ALR'2, Hg-X , T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, either cycloaryl, X is a halide, R "is fluoroalkyl, fluoroaryl, fluorocycloalkyl, or f luoroaralqui lo, and Z is a carboylate or tri-fluoroacetata. 22. A composition of the material of the formula (CnHL-MR '-R) m where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic fribila, substantially free of carbon deposited olotically. , the projection of the graphite layers in said fibrils extends a distance of at least two diameters of fibrils, n is ten integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', SiR'3, Si -OR '? And R' 3-y, Si4-0-SiR '2i- 0R', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, P 'is alkyl, aryl, cycloalkyl, alkyl, or cycloalkyl, X is a halide, R "is f-haloalkyl, fluoroaryl , f luoroc iclo Iqu i lo, or fluoro ra Iqui lo, and Z is a carboxylate or tri f luoroacet to. 23. A composition of the subject claimed in claim 22, wherein said fibril comprises cylindrical graphite sheets whose axes c are substantially perpendicular to their cylindrical axis. 24. A composition of the material claimed in claim 22, wherein the external diameter of said fibrils is less than about 0.1 μ. 25. A composition of the matter of the formula (CrtHL -) - (R '-R) m where the carbon atoms, Cn, are surface atoms of a fishbone bug, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR. ', SP.', SiR'3, Si-4-OR '-? - and R' 3-y, SÍ4-0-SÍR '2? - OR', R ", Li, ALR ' 2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, and haloalkyl, aralkyl, or aryl, X is a halu. r, P "is f luoroalkyl, fluoroaryl, luorocoyl, or radical fluorine, and Z is a carboxylate or tif luoroacet ta. 26. A composition of the matter of the formula (CnHL-í- (R'-A) m where the carbon atoms, Cn, are superficial carbons a graphitic nanotube, cylindrical substance that has a ratio between the length and diameter greater than 5 and diameter less than 0.5 μ, n is an integer, L is a number less than O.ln, m is ten less than 0.5n, each of R is alkyl, aryl, cycloalkyl, In either the cycle, A is selected within the group consisting of 0 0 0 0 I I I I 0Y, NHY, C-OY, C-NR'Y, C-SY, C-Y, -CR'2-0Y, N-Y, and C-Y, And it's an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, a glycoprotein, an antigen or an enzyme substrate, an enzyme inhibitor or the transition state analogue of an enzyme substrate or is selected from R ', - OH, R'-NH2, R'SH, R.'CHO, P.'CN, R'X, R'SiR'3, R'Si40R 'and R'3-y, R' Si40-SiR '2K3R', R'-R ", R'-N-CO, (C2H40 + WH, 4C3H60-h»? H, 4C2H40) w-r ', (C3H60)? -R' and R ', and is an integer equal or less than 3, P "is f luoroalkyl, fluaraaryl, f luorocycloalkyl, or f luoroa ra Iqui lo, X is a halide, and Z is a carboylate or trifluoroacetate, and w is a whole integer greater than 1 less than 200. 27. A composition of the material of the formula (CnHL * (R '-A) m where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic fibril substantially free of deposited carbon pi. As a matter of fact, the projection of the graphite layers in said fibrils extends at a distance of at least two fibril diameters, n is an integer, l. is a number less than O.ln, m is a number less than 0.5n, each of R is alkyl, aryl, cycloalkyl, aralkyl or cycloaryl A is selected from 0 0 0 0 0Y, NHY, C-0Y, C-NR'Y, C-SY, C-Y, -CR'2-0Y, N-Y, C, And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a glycoprotein, an oligonucleotide, an antigen or an enzyme substrate, an enzyme inhibitor or the transition state analog of a substrate of enzyme is either selected from R ', -OH, R'-NH2, R'SH, R'CHO, P'CN, R'X, R'SiR'3, P'Si40P' -) - and P'3 -y, R 'S? 40-SiR' 2 »aR ', R'-R", R'-N-CO, (C2H40-H.IH, 4C3H6C? -wH, C2H40) w-r', (C3H60 ) wR 'and R', and is an integer equal to or less than 3, R "is fluoroalkyl, fluoroaryl, f luoroc icloal or f luoroaralkyl, X is a hura, and Z is a carboxylate or well tif luoroacetate, and w is a whole number greater than 1 and less than 200. 28. A composition of the material claimed in claim 27, wherein said fibril comprises cylindrical graphitic sheets whose axes c are substantial; Ally perpendicular to its cylindrical axis. 29. A composition of the material claimed in claim 27, wherein the external diameter of said fibrils is less than about 0.1 μ. 30. A composition of the matter of the formula (CnHL-f (R'-A) where the carbon atoms, Cn, are surface atoms of a fishbone fibril, rt is an integer, L is a lower number to O.ln, m is a lower number than 0.5n, each of R is alkyl, aryl, cycloalkyl, aralkyl, or else aryl, A is selected from o o o o I I I I 0 Y NHY, C-OY, C-NR'Y, C-SY, C-Y, -CR'2-OY, N-Y, and c-Y, And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen or an enzyme substrate, an enzyme inhibitor or the transition state analog of a substrate of enzyme to either is selected from R ', -OH, R'-NH2, R * SH, R'CHO, R'CN, R'X, R'SiR'3, P'Si40R 'and R'3-y, P.' SÍ40-SÍR '2K) R', R'-R ", P .'- N-CO, (C2H40-ÍWH, 4C3H60 + wH,« C2H40 > w - r ', (C3H60) e »? - R' and R ', and is an integer equal to or less than 3, R" is f luoroalkyl, fluoroaryl, f luarocielsalqui lo, or f luo roa rl qui lo, X is a halide, and Z is a carboxylate or trifluoroacetate, and w is an upper whole number 1 and less than 200. 31. A composition of the material of the formula (CnHL * (X'-Ra) m wherein the carbon, Cn, are surface carbons of a substantially cylindrical graphitic nanotube having a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, n is an integer, L is a number less than O.ln , m is a number less than 0.5n, a is zero or an integer less than 10, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', SiR'3, SÍ4-0R '? And R' 3-y, Si-4-O-SiR '2-0P', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or cycloalkyl, X is a halide, X 'is a polynuclear aromatic, aromatic, polyteteranuclear or aromatic metalapolheteranuclea portion, R "is f loroalkyl, fluoroaryl, f luoroc ic ita, or f luo or l l, and Z is a carboylate to well tr if luoroacetate 32. A composition of the material of the formula (CnHL - (X'-Ra) m where the carbon atoms, Cn, are surface carbons of a substantially cylindrical, graphitic fibril, substantially free of deposited carbon, the projection of the graphite layers in said fibrils extends at a distance of at least two diameters of fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, a is zero, or an integer less than 10, each one of R is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR ', SiR'3, Si4-0R' - + yR'3-y, SÍ4-0-SÍR '2 * -0R', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or cyclane, X is a halide, X' is a polynuclear aromatic moiety, a polyhetero-nuclease aromatic moiety or an aromatic moiety metalopolheteronuclea, R "is a luoroalkyl, fluoroaryl, fluorine, or alkyl fluorine, and Z is a carbaxylate or tri-fluorouracetate 33. A composition of the material claimed in claim 32, wherein said fibril comprises cylindrical graphite sheets whose axes c are substantially perpendicular. to its cylindrical axis 34. A composition of the material claimed in claim 32, wherein the external diameter of said fibrils is less than 0.1 μm. 35. A composition of the matter of the formula (CnHL? - (X'-Ra) m where carbon atoms, Cn, are surface atoms of a fishbone fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, a is zero, or an integer less than 10, each of R is selected within the group consisting of S03H, C00H, NH2, OH, CHO, CN, COC, halide, COSH, SH, COOR ', SR', SiR'3, Si4-0R .'-? R'3-y, YES4-0-YES * 2 * -0R ', R ", Li, ALR'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or else C i.cloar i lo, X is a halide, X 'is a polynuclear aromatic moiety, a polyheteranuclear aromatic moiety or an aromatic metalopolhetheronuclear moiety, R "is a metalloalkyl, fluoroaryl, moallocycloalkyl, or a liquid moiety, and Z is a carboxylate or tri f Luoroacetate 36. A composition of the material of the formula (CnHL-MX'-Aa) wherein the carbon atoms, Cn, are surface carbons of a graphitic, substantially cylindrical nanotube having a ratio between length and diameter greater than 5 and a diameter less than 0.5 μ, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, a is an integer less than 10, each of A is select between 0 0 0 0 0Y, NHY, C I-0Y, CI-NR'Y, CI-SY, CI-Y, -CR'2-0Y, NY, and CY, And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen or an enzyme substrate, enzyme inhibitor or the transition state analog of a substrate of enzyme is either selected from P ', -OH, R'-NH2, P.'SH, P.'CHO, R'CN, R'X, R'SiR'3, R-SÍ40R' -ryP. '3-y, R' Si.40-SiR '2-H3R', R'-R ", R'-N-CO, (C2H40-H.1H, 4C3H60 wH, -4C2H40) wr ', (C3H60) wR' and R ', and is an integer equal to or less than 3, R' is alkyl, aryl, cycloalkyl, aralkyl, or cycloaryl , P. "is furoalkyl, fluoroaryl, fluoroalkyl, or 1-chloroquine, X is ten halide, X 'is a polynuclear aromatic moiety, a polyhetero-nuclease aromatic moiety or an aromatic metalopol-heteronuclear moiety, and: Z is a carboxylate or tif luoroacetate, and w is an upper whole number 1 and less than 200. 37. A composition of the material of the formula (CnHL X'-Aa) m where the carbon atoms, Cn, are surface carbons of a substantially cylindrical, graphitic fibril, substantially free of deposited carbon, the projection of the graphite layers in said fibrils extends over a distance of at least two diameters of fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, a is a whole number less than 10, each of A is selected from 0 0 0 or 0V, NHY, C-0V, ».Y,» _S ?, i-v, -CRC-OY. H. (And Y is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, a glycoprotein, an antigen or an enzyme substrate, enzyme inhibitor or analogue a transition state of an enzyme substrate or is selected from R ', -OH, R'-NH2, R'SH, R'CHO, R'CN, R'X, R'SiR'3, R'Si40R 'and R'3-y, R' Si40-SiR '2W3R', R'-R ", R'-N-CO, (C2H4CH-WH, 4C3H60-? H, -4C2H40) wr ', (C3H60) e. ? -R 'and R', and is an integer equal to less than 3, R 'is alkyl, aryl, alkylaryl, aralkyl, or cyclic, P "is faloroalkyl, fluoroa ryl, f luoroc It is either a fluoride, X 'is a polynuclear aromatic moiety, a polyheterogeneous aromatic moiety or an aromatic metalopolheteroortuclear moiety, Z is a carbaxylate or tri-fluoroulacetate, and w is an upper whole number 1 and less than 200. 38. A composition of the material claimed in the reiv indication 37, wherein said fibril comprises cylindrical graphite sheets whose axes c are substantially perpendicular to their. cylindrical shaft. 39. A composition of the material claimed in the research 37, where the external diameter of said fibrils is less than 0.1 μm. 40. A composition of the matter of the formula (CnHL (X'-Aa) m where the carbon atoms, Cn, are surface atoms of a fishbone fibril, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, a is a whole number less than 10, each of A is selected from 0 0 0 0 l i l i 0Y, NHY, C-OY, C-NR'Y, C-SY, C-Y, -CR'2-OY, N-Y, C-Y, And it is an appropriate functional group of a prstein, a peptide, an enzyme, an antibody, a nucleotide, a glycoprotein, an antigen or an enzyme substrate, enzyme inhibitor or the analogue of a transition state of an enzyme substrate is either selected from R ', -OH, R'-NH2, R'SH, R'CHO, R'CN, R'X, R'SiR'3, R'Si40R 'yP.'3-y, R' YES4-0-SIR '2-H3R', R'-R ", R'-N-CO, (C2H40 + wH, 4C3H60 * t? H, 4C2H40) w-r ', (C3H60) wR' and R ', and is an integer equal to or less than 3, R' is alkyl, aryl, cycloalkyl, aralkyla, or else ilo, R "is f luoroalqui It is a polynuclear aromatic moiety, an aromatic polyheteropetrophilic moiety, or a metallopal aromatic heterohequent moiety, Z is a carboxylate or tr if luoroacetate. , and M is a higher whole number 1 and less than 200. 41. A composition of the subject claimed in claims 31-40, wherein X 'is a phthalocyanine or parfirain. 42. A method for the formation of a composition of the matter of the formula (CnHL-H = i.m where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic nanotube, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of R is the same and is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide , COSH, SH, COOR ', SR.', SiR'3, YES4-0R '? -yP' 3-y, Si4-0-Si.R '2 + -OP.', R ", Li, ALR'2 , Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is alkyl, aryl, cycloalkyl, aralkyl, or cyclic, R "is f-alkyl, fluoroaryl, The fluorine is either a halide, and Z is a carboxylate or toluoroacetate, which comprises the step of reacting the surface carbons with an appropriate reagent under conditions sufficient to form nanotubes. that have the formula (CnHL) Rm. 43. A method for the formation of a composition of the matter of the formula. { CnHL-H = í.m where the carbon atoms Cn, are surface carbons of a graphitic nanotube, substantially cylindrical, n is a nil integer, L is a number less than O.ln and m is a number less than 0.5n, each of R is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP. ', SiR'3, Si 0R' andR'3-y ', YES40-SÍR' 2-KJR ', R ", Ll, AIR' 2, Hg-X, T1Z2 and Mg-X, and is a whole number equal to or less than 3, R 'is selected from alkyl, aryl, cycloalkyl, radical alkyl, cielaaryl, R "is a haloalkyl, fluoroaryl, f lusroc iclaalqui lo or f luoroa ralqui lo, X is a halide, 7. is carboxylate or tri fluoroaceta to, and further provided that when each of R is a group containing oxygen, COOH na is present, comprising the step of reacting the surface carbons with at least one suitable reagent under conditions sufficient to form functionalized nanotubes having the formula (CnHL-fRm 44. A method for the formation of a composition of the material of the formula CnHL -) - Rm where carbon atoms Cn, are surface carbons of a substantially cylindrical graphitic nanotube, n is an integer, L is a number less than O.ln and m is a number less than 0.5n, each of R is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCI, halide, COSH, SH, COOR ', SP', S? P'3, Si40R '* and R'3-y, Si40-SiR' 2 + OR, R ", Li, A1R'2, Hg- X, T1Z2 and Mg-X, and is an integer equal to or less than 3, R 'is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, cycloaryl , P "is a f luoroa Iqu i lo, fluoroarilo, f 1 uoracloloa Iqu i lo or f luoroaralqui lo, X is a halide, Z is carboxylate or tri fl uoacetate, and further provided that when each of R does not contain oxygen, it comprises the step of reacting the surface carbons with at least one appropriate reactive under conditions sufficient to form functionalized nanotubes having the formula (CnHL-) -Rm. 45. A method for the formation of a composition of the formula mate (CnHL-HA where the carbon atoms, Cn, are surface carbons of a graphitic nanotube, substantially cylindrical, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of A is selected from 0 0 0 0 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR '2-0Y, NY, and C-Y, And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of a substrate of enzyme is selected from R'-OH, R'-NH2, R'SH, R'CHO, P.'CN, R'X, R'SiR'3, R'-R ", R'-N -CO, (C2H40 *? H, 4C3H60? -IH, 4C2H40) wR ', (C2H60) wR' and R ', P.' is alkyl, aryl, cycloalkyl, aralkyl or cycloariol, R "is a f luoroa Iquilo, fluoroaryl, f luorooclo Iqui oob in flororo Iqui lo, X is a h lu.ro, Z is carboxylate or tri fi luaraacetata, and w is a whole number greater than 200, which comprises the steps of (a) it reacts the surface carbons with at least one appropriate reagent under conditions sufficient to form substituted nanotubes having the formula (CnHL -) - Rm, where each of R is the same and is selected from the group consisting of S03H, COOH, NH2, OH, CHO , CN, COCÍ, halide, COSH, SH, COOR ', SP.', SiR'3, Si 0R'-yyR'3-y, YES40-YES '2HDR, R ", Li, A1R'2, Hg- X , T1Z2 and Mg-X, and y is an integer equal to or less than? and 5 (b) reacting the substituted nanatubes (CnHL-y-Rm) with at least one suitable rectifier under conditions sufficient to form functionalized nanotubes having the formula (CnHL-fAm 46. A method for the formation of a composition of the material of the formula (CnHL-hA where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphitic nanotube, having a ratio between the length and diameter -5 greater than 5 and a diameter less than 0.1 miera, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of A is selected from OOO Ó / olili /, 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, / and • CY, Y is an appropriate functional group of a protein, urt peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, enzyme inhibitor. or the transition state analogue of an enzyme substrate is either selected from 'R'-OH, P'-NH2, R'SH, R'CHO, R'CN, R'X, R'SiP'3 , P '-P ", R'-N-CO, (C2H40-k»? H, 4C3H60? »? H, 4-C2H40) wP', (C2H60) eif-R 'and P', R 'is alkyl , arilo, c iclaa Iqu la i, ar lilo or ciel or rilo, P "is a luoroalqui lo, fluoroarilo, f lusroc ic loalqu lo or f luoro Iqui la, X is a halide, Z is c rbeDX i lato or tr if luoroaceta to, and t > ? is an integer greater than l less than 200, comprising the steps of: (a) reacting the surface carbons with at least one appropriate reagent under sufficient conditions to form nau.bos its products that have the. formula (CnHL -? * - Rm, where each of R is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP.', SiR '3, Si40R'-? > -yR'3-y, Si * 0-SiR' 2 0R, R ", Li, A1R'2, Hg-X, T1Z2 and Mg-X, and y is an equal integer or less than 35 and (b) reacting the substituted nanotubes (CnHL-Rm) with at least one appropriate reagent under conditions sufficient to form nanotubes with 1-ions that have the formula (CnHL- ^ Am. 47. Urt method for the formation of a composition of the matter of the formula (CnHL * -Am where the carbon atoms, Cn, are surface carbons of a graphitic nanotube, substantially cylindrical, substantially excen- carbon deposited pi role, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of A is selected from the group consisting of 0 0 0 0 IIII 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, V CY, Y is an appropriate functional group of a prodrug, a peptide, an enzyme, an antibody, an Igonucleotide, a t-nucleus, an antigen, or an enzyme substrate, an enzyme-inhibitor, or the transition state analogue of an enzyme substrate or is selected from R'- OH, R "-NH2, R'SH, R'CHO, R'CN, R'X, R'SiR'3, R'-R", R'-N-CO, (C2H40 - »- wH, C3H60- ) -e-? H, C2H40) w-R ', (C2H60) trP. 'and R', R 'is alkyl, aryl, cycloalkyl, aralkyl or cycloalkyl, R "is a luoroalkyl, f luoroar, f ororal or alkaline, X is a halide, 7. is carboxylate to trifluoroacetate, and is not an integer greater than 200, comprising the steps of: (a) reacting the surface carbons with at least one suitable reagent under sufficient conditions to form substituted nauotubes having the formula (CnHL ^ Rm, where each of R is the same and is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN., COCÍ, halide, COSH, SH , COOR ', SR ', SiP'3, Si40R' + yR'3-y, Si-40-Si.R '2-K3R, R ", Li, A1R'2, Hg- X, T1Z2 and Mg-X, and y is a whole number equal to or less than 3; and ib) reacting the substituted nanotubes (CnHL-fr-Rm with at least one suitable rectifier under conditions sufficient to form fungal ionized nanotubes having the formula (CnHL Am. 48. A method for the formation of a composition of the matter of the formula (CnHL-hAm dande carbon atoms, Cn, are superficial carbons of a graphitic nanotube, substantially cylindrical, n is an integer, L is a number less than O.ln, m is a number lower- to 0.5n, each of A is selected within the group consisting of 0 0 0 0 IIII 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, and C "?, * Y is an appropriate functional group of protein dinner, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or alternatively the transition state analog of a substrate in ima is selected from P'-OH, P'-NH2, R'SH, R'CHO, P'CN, R'X, R'SiR'3 , R'-P ", R'-N-CO, (C2H40 -KnH, "fC3H60 -) - wH, 4C2H40)? -P ', (C2H60) mR' and R ', P' is alkyl, arda, cycloalkyl, aralkyl or cycloalkyl, P" is a haloalkyl, fluoroaryl, f luoroc icloalqui or fluaroa ralqui lo, X is a halide, Z is carba ilato or tr if luoroacet o, y? is an integer greater than 1 and less than 200, comprising the step of reacting substituted nanotubes (CnHL - ^ - Rm with at least one appropriate rectifier under conditions sufficient to form functionalized nanatubes having the formula (CpHL- ^ -Am, where each of P is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, h l .., COSH, SH, C00P ', SP', SiP'3, Si40R '? - yP'3-y, YES4Í3-SYP 2- NDP, P ", Li, A1P'2, Hg-X, T1Z2 and Mg-X, and y is an integer equal to or less than 3. 49. A method for the formation of a composition of the material of the formula (CnHL m where carbon atoms, Cn, are surface carbons of a substantially cylindrical graphene, having a ratio between length and diameter greater than 5 and a diameter smaller than 0.1 miera, n is an integer, L is a number less than O.ln, m is a number less than 0.5n, each of A is selected within the group consisting of 0 0 0 0 0Y, NHY, C-OY, C-NR'Y, C-SY, C-Y. -CR '"" 0 * »N" Y' CY, and is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, inhibitor ci in ima or the transition state analogue of an enzyme substrate or is selected from R'-OH, R'-NH 2, R 'SH, R'CHO, R' CN, R 'X, R'SiR. '3, R'-R ", R'-N-CO, (C2H40 ?? H, 4C3H60 + wH, 4C2H40) ui-R ', (C2H60) e-? ~ R' and P. ', R' is alkyl, aryl, cycloalkyl. It is either aralkyl or fl awary, R "is furoalkyl, fluoroaryl, f luorocloalkyl or f 1uor 1a, 1 is a halu.ro, Z is carba tyl or tri f luoroacetate, ywe = an upper whole number l less than 200, which comprises the step of reacting substituted nanotubes (CnHL- ^ Pm with at least one suitable rectifier under conditions sufficient to form functionalized nanotubes having the formula (CnHL) Am , where each of P is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', SiP'3, Si- "3P'- VyR * 3-y, Si40-SiP '2-HDR, P ", Li, A1R'2, Hg-X, T1Z2 and Mg-X, and y is an integer equal to or less than 50. A method for the formation of a composition of the material of the formula fCnHL-Wta where the carbon atoms, Cn, are surface carbons of a graphitic panotube, substantially the cylindrical mind, substantially ex- posed of carbon deposited p i. ru1 i t i cally, n is an integer number, L is urt number i nferior to O. l n, m is a number less than < D .5n, each of A is selected from the group consisting of 0 0 0 0 I I I I 0Y, NHY, C-OY, C-NR 'Y, C-SY, C-Y, -CR'2-0Y, N-Y, and And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, an enzyme inhibitor, or the transition state analogue of a substrate. of enzyme or bi n is selected from the group that cinsiste of P'-OH, R'-NH 2, R'SH, P'CHO, R'CN, R'X, R'SiR'3, R'-P " , R'-N-CO, (C2H40 wH, C3H60 u? H, 4C2H40) u? -R ', (C2H60) wR' and R ', P' is alkyl, aryl, cycloalkyl, aralkyl or c lo lo lo lo, P "is f luoroa l lo lo, fluoroaryl, f luoroc iclo lqui lo or else f luoroa ral qui lo, X is a h lu.ro, Z is carboxylate to tri f lusroacet to, and eu is a number Whole integer is less than 200, which comprises the step of reacting substituted nanotubes (CnHL-p) with at least one suitable rectifier under conditions sufficient to form functionally functioning nanotubes having the formula (CnHL) Am, where each of R is selected within the group consisting of S03H, COOH , NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SR', SiR'3, Si.40R '-) - and R'3-y, Si40-SiR' 2-H3R, R " , Li, AIR'2, Hg-X, T1Z2 and Mg-X, and y is an integer equal to or less than 3. 51. A method for forming dinner co-position of the material of the formula (CnHL-R '-R) m where carbon atoms, Cn, are surface carbons of a graphitic nanotube, cylindrical substance, n is an integer, L is a number less than O.ln, m is a number less than 0.5n , each of R is selected within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOP ', SP ', SiR'3, Si40R' and R'3-y, YES40-YESP '2H3P, R ", Li, A1R'2, Hg- X, T1Z2 and Mg-X, and is an integer equal to or less than 3 P 'is alkyl, aryl, cycloalkyl, aralkyl or cycloalkyl, X is a halide, R "is f luoro l, lo, fluoroaryl, f luoroc icl or f or lor a ra l, 7 is carboxylate otif 1 uoroac tato, comprising the steps of: (a) deogenating * the graphitic nanotubes under conditions sufficient to form deoxygenated nanotubes; and (b) reacting the desogenated nartotubes with at least one suitable activated olefin under conditions sufficient to form functionalized nanotubes having the formula (CnHL-WP '-P) m. 52. A method for the formation of a composition of the matter of the formula (CnHL-MR'-A) m where the carbon atoms, Cn, are surface carbons of a substantially cylindrical graphene nanotube, n is a integer, L is a number less than O.ln, m is a number lower than 0.5n, P 'is alkyl, aplo, c iclaal qu i lo, aralkyl or cycloal yl, X is a halide, each of A is selected within] group consisting of 0 0 0 0 0Y, NHY, C 1 -OY, C I-NR'Y, C I-SY, CI-Y, -CR'2-0Y, N-Y, and c-Y | And it is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of a substrate of enzyme to either is selected from P'-OH, P '~ NH2, R'SH, P'CHO, P'CN, P'X, P'SiP'3, P'-P ", P'-N- C0, (C2H4D-u? H, 4 3h60 »wH, 4C2H40) w-R ', (C2H60) e-¡-P' and P ', P" is fluoroalkyl, fluoroplast, fluoroalkyl or f luoro ralqui lo, and Z is carboxylate otif luoroacetate, comprising the steps of: (a) dissociating the graphitic nanotubes under conditions sufficient to form deoxygenated nanotubes; and ib) reacting the n-deoxygenated notubes with at least one suitable activated olefin to form substituted nanotubes having the formula (CnHL-WR '-R) m, wherein each of R is selected from S03H, COOH, NH2, OH , CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP. ', SiR'3, S i + 0R' and R * 3-y, Si40-SiR '2K3R, R ", Li, AIR' 2, Hg- X, T1Z2 and Mg-X, and y is a whole number equal to or less than to 3; and (c) reacting the substituted nanotubes having the formula (CnHL-WR '-R) m with at least one appropriate reagent under conditions sufficient to form fcene ionsanized nanotubes having the formula (CnHL-R' -A) m . 53A method for the formation of a composition of the formula (CnHL-P'-A) m where the carbon atoms, Cn ^ are surface carbons of a graphitic, substantially cylindrical nanotube, r, is a number whole, L is a number less than O.ln, m is a number less than 0.5n, R 'is alkyl, aryl, haloalkyl, aralkyl or heavenly, X is a halide, each of A is selected within of the rump consisting of 0 0 0 0 1 1 II 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, and CY, Y is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analogue of an enzyme substrate, or select between R'-OH, R'-NH2, R'SH, P'CHO, R'CN, R'X, R'SiR'3, R'-R ", R'-N-CO, (C2H40- H? H, 4c3h60-H? H, -fC2H40)? -R ', (C2H60) u >; -R 'and R', R "is f -alloalkyl, fluoroaryl, f luoroc ic or l-lo l or f lo-lo l, and 7 is carboxylate otrif luoroacet or, which comprises the step of reacting substituted nanotubes which they have the formula (CnHL- .P. '-R) m with at least one appropriate reactive under conditions sufficient to form functionalized nanotubes having the formula (CnHL-R' -A) m, where each of P it is selected from S03H, COOH, NH2, OH, CHO, CN, COCÍ, halu.ro, COSH, SH, COOR ', SP.', SiR'3, Si-íOP. 'and R'3-y, Si 0- Si.P. '2H3R, R ", Li, AIR' 2, Hg-X, T1Z2 and Mg-X, and y is an integer equal to or less than -T 54. A method for the formation of a composition of the matter of the formula (CnHL-X'-Ra) rrt where the carbon atoms, Cn, are ca surface bonds of a substantially cylindrical graphitic nanotube, n is a whole number, L is a number less than O.ln, m is a number less than 0.5n, a is zero, or an integer less than 10, each of P e selects within the group consisting of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP', SiP'3, SI40P '+ and P'3-y, Si 0-SiP' 2) P, ", Li, A1R'2, Hg- X, T1Z2 and My-X, and is an integer equal to or less than 3 R 'is alkyl, aryl, cycloalkyl, aralkyl or cycloalkyl, X is a halide or X 'is a polynuclear aromatic moiety, a polyhetero-nuclease aromatic moiety, or a portion of the aromatic etalopolhetheronuclear portion, P "is a fluoride, a fluoroaryl, a fluoride or a fluorine, and Z is caboxy or tr or 1 eeoroaceto, which comprises the step of adsorbing at least one appropriate macracyclic compound on the surface of the graphitic nanotube under sufficient conditions to form a functionalized nanotube that has the formula (CnHL) (X '-Pa) m. 55. A method for the formation of a composition of the matter of the formula (CnHL? - (X'-Aa) m where the carbon atoms * - », Cn, are surface carbons of a graphitic nanotube, substantially cylindrical, n is an integer, L is a number less than 0.1n, m is a number less than 0.5n, a is a whole number less than 10, each of A is selected within the group consisting of 0 0 0 0 I I I I 0Y, NHY, C-OY, C-NR'Y, C-SY, C-Y, -CR'2-0Y, N-Y, and C-Y, And it is a functional group aprópiado of a protein, a peptide, an enzyme, an antibody, an IgG, a nucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of a substrate of enzyme or is selected from R'-OH, R'-NH2, R'SH, P'CHO, R'CN, P'X, R'SiR'3, R'-R ", R'-N-CO, (C2H4C? -wH, 4. .. 3h60 -) -? H, 4C2H40)? -P ', (C2H60) wR' and P ', P' is alkyl, aryl, cycloalkyl, aralkyl or either ci: 1 or ryl, R "is f luoroalkyl , fluoroaryl, f luorocycloalkyl, or else, where X is a ha 1. uro, X 'is a polynuclear aromatic moiety, a polyhetero-nuclease aromatic moiety or an aromatic moiety meta 1 opo 1 i het eroncee r, Z is carba ilato otrif luoroaceta to, and m is an integer greater than 1 and less than 200, comprising the steps of: (a) adsorbing at least one appropriate macrocyclic compound on the surface of the graphitic nanotube under conditions sufficient to form a substituted nanotube having the formula (CnHL) (X '-Pz) m, where each of R is the same and is selected from the group with S03H iste, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP', SiP'3, SI40R '* and P'3-y, Si40-SiP' 2-H3R, P ", Li, A1R'2, Hg- X, T1Z2 and Mg- X, yy is a whole number equal to or less than, 3; and < b) reacting the substituted nanotubes (CnHL X'-Ra) m with at least one appropriate reagent under its conditions to form a functionalized nanotube which has a polymer (CnHL.-). - (X '-Aa) m 56. A method for the formation of a composition of the mai-ei-id of the formula (CnHL-M' -Aa) m where the carbon atoms, Cn, are surface carbons of a graphitic nanotube, a cylindrical substance, where n is an enter number, L is a number less than O.ln, m is a number less than 0.5n, a is an integer less than 10, each of A is selected Within the group consisting of 0 0 0 0 IIII 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, and CY, Y is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, an oligonucleotide, a nucleotide, an antigen, an enzyme substrate, enzyme inhibitor or the transition state analogue of an enzyme substrate, or select between P'-OH, R'-NH2, P'SH, P'CHO, P'CN, P'X, P'SiR'3, R'-P ", P'-N-CO, (C2H40 wH, c3h60 + wH, 4C2H40 ) w R ', (C2H60) u? -R' and P ', P' is alkyl, to ilo, to the alkali, to aralkyl to either c ic 1 or to ilo, P "is f luoroalkyl, fluoroaryl, f] uoroe icloalqui lo or f luoroa r Iqui lo, X is a halide, X 'is a polynuclear aromatic portion, a poly aromatic portion is heterogeneous or an aromatic portion metalopolyhetheronucl, 7 is carboxylate otrif luoroacet, and -I is an integer greater than 1 and less than 2 0, comprising the step of reacting the substituted nanotubes (CnHL-i '- (X' -Ra) m with at least one appropriate reagent under conditions sufficient to form a nanotubo fune iortal i zado that has the formula (CnHL) í X '-Aa) m, where each of P is the same and is selected within the group that with iste of S03H, COOH, NH2, OH, CHO, CN, COCÍ, halide, COSH, SH, COOR ', SP', SiR'3, SI-fiOP '? - yP'3-y, Si? O-SiP' 2HDR, P ", Li, A1P'2, Hg- X , T1Z2 and Mg-X, and y is an integer equal to or less than * 3. 57. A method in accordance with that claimed in claims 54 or 55, where before the adsorption step on the surface carbons, the graphitic nanotubes are scatter in a medium. 58. A method according to claims 42, 43, 44, 45, 46 or 47, wherein before the step of reacting the surface carbons, the graphitic nanotubes are dispersed in a medium. 59. A method according to claim 3 in claims 45, 46, 47, 48, 49, 50, 52, 53, 55 or 56, wherein before the step of reacting the substituted nanotubes with a reagent, the nanotubes are dispersed replaced in a medium. 60. A method according to claim 42, 43, 44, 45, 46, or 47, wherein the step of reacting the surface carbons comprises sulphonation of the surface carbons. 61. A method as claimed in claim 42, 43, 44, 45, 46, 47, 48, 49 or 50, wherein the step of reacting the surface carbons comprises metallizing the surface materials with a reactant. organometallic 62. The method according to claim 47 or 50, wherein the projection of the graphite layers in said napho tubes extends over a distance of at least two nanotube diameters. 63. The method according to l a =, claims 47 or 50, wherein said nanotube comprises cylindrical graphitic sheets whose axes c are substantially perpendicular to their cylindrical axis. 64. The method of compliance with that claimed in rei indications 47 or 50, where the external meter of said nanotube is less than 0.1 miera. 65. The method according to claim 47 or 50, wherein the carbon atoms carbon Cn, are surface atoms of fishbone fibrin-eilaine. 66. A method for introducing functional groups on the surface of carbon nanotubes to form a powered nanotube having the formula (CnHL-y-Am where the carbon atoms, Cn, are surface carbons of a graphitic nanotube). , substantially cylindrical, substantially free of carbon deposited irtically, n is a whole number, L is a number less than O.ln, m is a number less than 0.5n, each of A is selects within the rump that with inte of 0 0 0 0 IIII 0Y, NHY, C-OY, C-NR'Y, C-SY, CY, -CR'2-0Y, NY, and CY, Y is a functional group appropriate for a protein, a peptide, an enzyme, an anticuet-po, an oligonucleotide, a nucleotide, an antigen, or an enzyme substrate, an enzyme inhibitor, or the transition state analog of a substrate of enzyme is either selected from the group consisting of P'-OH, R'-NH2, R'SH, P'CHO, R'CN, P'X, P'S? P'3, R'-R ", R'-N-CO, <; C2H40 * -mH, 4c3h60 nH, 4C2H40) w-R ', (C2H60) u? -P' and R ', P' is alkyl, aryl, cycloalkyl, aralkyl or elselary, P "is a luoroalkyl i 1, f luoroarlo, f luoroc ic loalqui lo or f luoroa r Iqu i lo, X is a halide, Z is c rboxylate or r and f, and in is a whole number greater than 200, comprising the steps of: (a) contacting the carbon fibrils with selected oxidizing agents within the group including a solution of an alkali metal chlorate in a strong acid for a period of time sufficient to oxidize the surface of said fibrils, and ib) contacting the surface-oxidized carbon fibrils with a suitable reagent to add a functional group to the surface of the carbon fibrils 67. A method according to claim 66, wherein the carbon fibrils are subjected to processing before being in contact with oxidizing agents. 68. A method of compliance with what is claimed in the rei indication 66, where the process comprises the dispersion of the carbon fibrils in a solvent. 69. A method of confrmity with that claimed in claim 68, where after being dispersed in the solvent, the carbon fibrils are filtered and dried. 70. A method according to claim as claimed in claim 66, wherein the alkali metal chlorate is sodium chlorate or bi n potassium chlorate. 71. A method of conformance with that claimed in claim 66, wherein the strong acid is sulfuric acid. 72. A method of conformity-with what is claimed in the rei indication 66, where the group functions] added to the superficially oxidized fibrils is if wool of 1 to 1/1, 73. A method in accordance with that claimed in claim 66, wherein the functional group added to the fibrils or; superficially driven < It is a group that makes it long chain. 74. A method according to claim as claimed in claim 66, wherein the functional group added to the fibrils or idadas is a long-chain hydroxyl group. 75. Urt method according to claim as claimed in claim 66, wherein the functional group added to the fibrils or idadas superficially and a long chain amine group. 76. A method of conformance with that claimed in rei indication 66, wherein the functional group added to the superficially oxidized fibrils is a 1-carboncarbon. 77. A method according to claim 66, wherein the sufficient time for oxidation is between apiro: immately 0.5 hours and 24 hours. 78. A network of fibrils fune on 1 i adas comprising at least 2 functional fibrils linked in functional groups either by * means of 1 or several direct bonds or at least by means of a linker portion, where said linker portion is either bi functional or functional polynnal. 79. A composition of the material of the formula (FF) linker (FF) where the linker is a bi-functional portion or polyfunction linked to an appropriate fibrilay fi nase 1 (FF), derived from ls following fibrilas sust i tu i da: < v > [C "HL [R'-R] m (v> [CnHt4 [R'-A) m; < vi > [C "HL4. [X'-Ra] m; and (vii) tCnHL * [X'-Aa) m? where the carbon atoms, Cn, are super fi cial carbons of a graphitic nanotube, n is a whole number, L is a number less than O.ln, m is a number less than 0.5n, a is zero or a whole number At least each of P is selected from the group consisting of S03H, COOH, NH2, OH, CHO, CN, COC, halide, COSH, SH, C00P ', SP', S? P'3, SI40P ' yP'3-y, Si + O-SiF '2H3P, R ", Li, A? B'2, Hg-X, T1Z2 and Mg-X, and is an integer equal to or less than 3, A is selected within of the group that consists of 0 0 0 0 l i l i Y, NHY, C-OY, C-NR'Y, C-SY, C-Y, -CR'2-0Y, N-Y, and C-Y, And it is a functional group appropriate to a protein, a peptide, an enzyme, an antibody, a glycoprotein, a nucleotide, an antigen, or an enzyme substrate, an inhibitor of in ima to the state logo of transition of an enzyme substrate or is selected from the group consisting of R'-OH, P'-NH2, P'SH, P'CHO, R'CN, P'X, R'SiP'3, R '-R ", R'-N-CO, (C2H40) wH, (c3h60) t» H, (C2H40) wP', (C2H60)? -P 'and R', P 'is alkyl, aplo, cycloalkyl The aralkyl or cyclalamp, P "is a luoroalkyl, fluaroaplo, f luoroocloyl or a lorazele, X is a halide, X 'is a polynuclear aromatic moiety, a polyhetero nuclease aromatic moiety or a moiety aromatic metalopal ihet ranuc lear, Z is carboxylate or ri f luoroacet to, and ni is an integer greater than 1 and less than 200, 6 < "*" A method for the production of a network of carbon fibrils comprising the poetry in contact of carbon fibrils with a strong oxidizing agent for a period of time sufficient to oxidize the surface of said carbon fibrils; said fibrils superficially oxidized with a suitable reagent to add a functional group on the surface of the carbon fibrils, and in addition contacting said functional fibrils super fi cially with an amount of an effective crosslinking agent for the production of carbon fibers. A network of carbon fibrils Bl. A method for the production of a carbon fibril network comprising the steps of: (a) contacting the fibrils with a solution of an alkali metal chlorate in a strong hydrochloride. for a period of time sufficient to oxidize the surface of said fibrils; (b) contacting the surface oxidized fibrils with a suitable reagent to add a functional group to the surface of the carbon fibrils; and (c) further contacting said functionalized fibrils with an effective amount of re-icing agent. 82. A method according to that claimed in the rei indications 81 or 82, wherein the crosslinking agent is a diol or a diamine. 83. A method for the production of a carbon fibril network comprising contacting the carbon fibrils with a strong oxidizing agent for a sufficient period of time to oxidize the surface of said carbon fibrils and bring them into contact said fibrils surfacely oxidized with an amount of an effective crosslinking agent to produce a network of carbon fibrils, 84. A method as claimed in claim 83, wherein the strong agent or promoter e. an alkali metal chlorate or nitric acid. 85. Urt method according to claim as claimed in claim 83, wherein the crosslinking agent is a polyol or a paliamine. 86. A method for the production of a network of functionalized fibrils comprising the reaction of at least two fibrils fceneionally with a linker portion comprising a bifunctional or palpational function. 87. A superficially functioning fungal fibril 1 formed by the method comprising the steps of contacting the carbon fibrils with an effective amount of strong oxidizing agent for a period of time sufficient to oxidize the surface of the carbon fiber. said fibrils; and contacting said fibrils with a suitable reagent to add a functional group on the surface of said fibrils. 88. A surface mobilized carbon fibril comprising a carbon fibril whose surface is uniformly substituted with a functional group nori l. 89. } The carbon fibril is modified super fi cially in accordance with that claimed in claim 88, wherein the functional group is carboxyl. 90. A method for uniformly replacing the surface of the carbon fiber with a functional group comprising the contact of the carbon fibrils with an effective amount of reactive reactant capable of uniformly isolating a group. functional on the surface of said carbon fibrils. 91. A method for uniformly replacing the surface of carbon fibrils with a functional group as claimed in claim 90, wherein the functional group is carboxylol 92. A method of conforming to that claimed in claim 90, wherein the Reagent is a functional fungicidal porphyrin. 93. A method according to claim 90, wherein the reagent is a phthalocyanine. 94. A method according to claim 93, wherein the phthalocyanine is cobalt phthalocyanine. 95. A modified carbon fibride suprafially elaborated by means of the method comprising the contacting of carbon fibrils with an effective amount of a reactant to form a functional group on the surface of said carbon fibrils. . 96. A carbon fibril surface-modified according to 1 i i i i i i i i i i n i i n i 95, where the reactive is a porphyrin func iona 1 i z da. 97. A surface modified carbon fiber with consistency with claim 96, wherein the reagent is a phthalocyanine. 98. A carbon fibril surface modified according to the indication 97, where the phthalocyanine is cobalt f alocianin. 9 ?. A network of carbon fibrils formed by the method comprising the steps of: (a) contacting fibrils with an oxidizing agent for a sufficient period of time to oxidize the surface of said fibrils; < b) contacting the surface-oxidized fibrils with suitable reagent to add a functional group to the surface of the fibrils, and (c) contacting said superficially functionalized fibrils with an effective amount of a reagent agent. No. 1 0. An electrode comprising nanotubes operates 1 i.

1. An electrode in accordance with that claimed in claim 10, wherein the nanotubes funi oned are nanotubes substituted by f t 1 or the child. 10

2. A reinforced ceramic material comprising rt3 noted scattered func tionals in a material of scale. 10

3. A refractory ceramic material produced by the dispersion of a functional nanotube in an accu- rate solution > 3 which contains a precursor that can be hydrolyzed from the ceramic material and the conversion of the precursor to the i-rol i abl e in a reinforced ceramic material. 10

4. A method for making a ceramic reinforced material comprising the dispersion of a funeled canvas nanotube placed in an ecosa solution containing a hydrolysable precursor of a ceramic matrix material and the conversion of the hydololysable precursor into a reinforced material of ceramics. 1

5. A colloidal solution gel material comprising the nanotubes operates 1 i. 10

6. A porous material comprising numerous networks of functionalized nanotubes as defined in claim 78, ions 78 or bi n 79. 10

7. A ma terial adsorbent comprises the porous material of claim 103. 10

8. A catalyst support material comprising the porous element of l rei indication 103. 1

9. A "medium of a topography medium comprising the iiiite? > of the claim 103,