MX2008004879A - Composite nanoparticles, nanoparticles and methods for producing same - Google Patents

Abstract

In various aspects provided are methods for producing a nanoparticle within a cross-linked, collapsed polymeric material, saidmethod including (a) providing a polymeric solution comprising a polymeric material;(b) collapsing at least a portion of the polymeric material about one or more precursor moieties;(c)cross-linking the polymeric material;(d) modifying at least a portion of said precursor moieties to form one or more nanoparticles and thereby forming a composite nanoparticle. In various embodiments, a non-confined nanoparticle can be produced by complete pyrolysis of the confined nanoparticle, and a carbon-coated nanoparticle by incomplete pyrolysis of the confined nanoparticle.

Description

COMPOSITE NANOPARTICLES, NANOPARTICLES AND METHODS FOR THE PRODUCTION OF THE SAME FIELD OF THE INVENTION The invention relates to methods for producing composite nanoparticles comprising nanoparticles confined within collapsed, crosslinked polymers, and nanoparticles per se, - the composite nanoparticles, nanoparticles and nanoparticles coated with carbon.

BACKGROUND OF THE INVENTION Nanoparticles are nano-sized materials, for example, metals, semiconductors, polymers and the like, which possess unique characteristics due to their small size. The nanoparticles in aqueous and non-aqueous solvents can be synthesized using a variety of methods. The conformation of a polymer in solution is dictated by various conditions of the solution, including its interaction with the solvent, its concentration and the concentration of other species that may be present. The polymer can undergo conformational changes depending on the pH, the ionic strength, the crosslinking agents, the temperature and the concentration. For polyelectrolytes, at high charge density, for example, when the "monomeric" Ref. 192061 units of the polymer are fully charged, an extended conformation is adopted due to the electrostatic repulsion between similarly charged monomeric units. The decrease in the charge density of the polymer, either through the addition of salts or a change in pH, can result in a transition from the extended polymer chains to a more tightly packaged, eg collapsed, globular conformation. The collapse transition is driven by the attractive interactions between polymer segments that cancel or counteract electrostatic repulsion forces at sufficiently small charge densities. A similar transition can be induced by changing the solvent environment of the polymer. This collapsed polymer is itself of nanoscale dimensions and by itself, is a nanoparticle. In this specification and in the claims the term "collapsed polymer" refers to an approximately globular shape, generally as a spheroid, but also as a collapsed polymer of elongated or multi-lobed conformation, having nanometric dimensions. This collapsed conformation can be made irreversible by the formation of intramolecular chemical bonds between the segments of the collapsed polymer, for example by cross-linking. Macromolecules, for example, polymers with appropriate functional groups may undergo inter- or intra-molecular crosslinking reactions to produce new materials or new molecules with different properties, such as, for example, form, solubility, thermal stability and density. These reactions are important in the preparation of new materials and various schemes for the chemical reactions that lead to cross-linking, which are described in the literature, for example, U.S. Patent No. 5,783,626-Taylor et al., Issued on July 21, 1998, describes a chemical method for crosslinking polymers with allyl functional group in the latex form, containing portions of enamine and protruding methacrylate groups, via a free radical crosslinking reaction during film formation producing coatings with superior solvent resistance and increased thermal stability. The polymeric crosslinking has also been used to stabilize semiconductor and metal nanoparticles. U.S. Patent No. 6,872,450-Liu et al, issued March 29, 2005, teaches a method for stabilizing surface-coated semiconductor nanoparticles by self-assembly of the two-block polymers on the surface coating and cross-linking the groups functional on the two-block polymer. Similarly, U.S. Pat. No. 6, 649, 138 - Adams et al., Issued November 18, 2003, describes how branched amphiphatic dispersants, coated on hydrophobic nanoparticles, can also be crosslinked to form a cohesive, permanent top coat around the nanoparticle. The chemical crosslinking means may be through radical reactions of the overhang groups containing unsaturated bonds as described in U.S. Patent No. 5,783,626. Yet another method is through the use of molecules having multifunctional groups that can react with the functional groups of the polymer as described in U.S. Patent Nos. 6,649, 138 and 6,872,450. Alternatively, crosslinking can be achieved through high energy radiation, such as gamma radiation. The most common method of preparing chalcogenide semiconductor nanocrystals is the TOP / TOPO synthesis (CB Murray, DJ Norris, and MG Bawendi, "Synthesis and Characterization of Nearly Monodisperse CdE (E = S, Se, Te) Semiconductor Nanocrystallites," J Am. Chem. Soc, 115: 8706-8715, 1993). However, this method again involves multiple chemical steps and large volumes of expensive and toxic organometallic metallic precursors, and organic solvents. In addition, such nanoparticles need to be chemically modified in order to make them soluble in aqueous solution, which is important for a number of applications. The chalcogenide nanoparticles have also been synthesized in aqueous solution at low temperature using water soluble thiols as stabilizing agents ((a) Rajh, OL Miéié, and AJ Nozik, "Synthesis and Characterization of Surface-Modified Colloidal CdTe Quantum Dots," J. Phys. Chem., 97: 11999-12003, 1993. (b) AL Rogach, L. Ktsikas, A. Kornowski, D. Su. A. Eychmüller, and H. Weller, "Synthesis and Characterization of Thiol-Stabilized CdTe Nanocrystals, "Ber. Bunsenges, Phys. Chem., 100 (11): 1772-1778, 1996. (c) A. Rogach, S. Kershaw, M. Burt, M. Harrison, A. Kornowski, A. Eychmüller , and H. Weller, "Colloidally Prepared HgTe Nanocrystals with Strong Room-Temperature Infrared Luminescence," Adv. Mater. 11: 552-555, 1999. (d) Gaponik, N., DV Talapin, AL Rogach, K. Hoppe, EV Shevchencko, A. Kornowski, A. Eychmüller, H. Weller, "Thiol-capping of CdTe nanocrystals: an alternative to organometallic synthetic routes," Journal of Physical Chemistry B, 2002, Vol 106, iss. 39, p. 7177-7185. (e) A.L. Rogach, A. Kornowski, M. Gao, A. Eychmüller, and H. Weller, "Synthesis and Characterization of a Size Series of Extremely Small Thiol-Stabilized CdSe Nanocrystals," J. Phys. Chem. B. 103: 3065-3069 , 1999). However, this method generally requires the use of an inert atmosphere with multiple steps of processing and production of precursor gases. Another water-based synthesis involves the formation of undesirable byproducts that must first be eliminated before the semiconductor particles can be obtained (H. Zhnag, Z. Hou, B. Yang, and M. Gao, "The Influence of Carboxyl Groups on the Photoluminescence of Mercaptocarboxylic Acid-Stabilized Nanoparticles, "J. Phys. Chem. B, 107: 8-13, 2003). It is known that CdTe nanocrystals have tunable luminescence from green to red and have shown tremendous potential in thin light emitting films (AA Mamedov, A. Belov, M. Giersig, NN Amedova, and NA Kotov, "Nanorainbows: Graded Semiconductor Films from Quantum Dots, "J. Am. Chem. Soc, 123: 7738-7739, 2001), photonic crystals (A. Rogach, A. Susha, F. Caruso, G. Sukhoukov, A. Kornowski, S. Kershaw, H. Móhwald, A. Eych üller, and H. Weller, "Nano- and Microengineering: Three-Dimensinoal Colloidal Photonic Crystals Prepared from Submicrometer-Sized Polystyrene Spheres Latex Pre-Coated with Luminescent Polyelectrolyte / Nanocrystal Shells," Adv. Mater. 12: 333-337, 2000), and biological applications (NN Memedova and NA Kotov, "Albumin-CdTe Nanoparticle Bioconjugates: Preparation, Structure, and Interunit Energy Transfer with Antenna Effect," Nano Lett., 1 (6): 281-286, 2001). The PbTe and Hgte materials show tuneable emission in the infrared and look promising in the telecommunications industry. Hgte nanoparticles have been incorporated into more sophisticated assemblies, particularly as components in thin film electroluminescent devices ((a) AL Rogach, DS Koktysh, M. Harrison, and NA Kotov, "Layer-by-Layer Assembled Films of HgTe Nanocrystals with Strong Infrared Emission, "Chem. Mater., 12: 1526-1528, 2000. (b) E. O'Conno, A. O'Riordan, H. Doyle, S. oynihan, A. Cuddihy, and G. Redmond, "Near-Infrared Electroluminescent Devices Based on Colloidal HgTe Quantum Dot Arrays," Ap l. Phys. Lett., 86: 2011-14-1-20114-3, 2005. (c) MV Kovalenko, E. Kaufmann, D. Pachinger, J. Roither, H. Huber, J. Stang, G. Hesser, F. Scháffler, and W. Heiss, "Colloidal HgTe Nanocrystals with Widely Tunable Narrow Band Gap Energies: From Telecommunications to Molecular Vibrations," J. Am. Chem Soc, 128: 3516-3517, 2006) or solar cells (S. Gimes, H. Neugebauer, NS Sariiciftci, J. Roither, M. Kovalenko, G. Pillwein, and .Hiss, "Hybrid Solar Cells Using HgTe Nanocrystals and Nanoporous Ti02 Electrodes, "Adv. Funct. Mater. 16: 1095-1099, 2006). PbTe, on the other hand, can be developed in a variety of glass at high temperatures to produce composite materials for optoelectronic device applications ((a) AF Craievich, OL Alves, and LC Barbosa, "Formation and Growth of Semiconductor PbTe Nanocrystals in a Borosilicate Glass Matrix, "J. Ap l.

Cryst., 30: 623-627, 1997. (b) V.C.S. Reynoso, A.M. by Paula, R.F. Cuevas, J.A. Medeiros Neto, O.L. Alves, CL. Cesar, and L.C. Barbosa, "PbTe Quantum Dot Doped Glasses with Absorption Edge in the 1.5 pm Wavelength Region," Electron. Lett., 31 (12): 1013-1015, 1995). The doping of CdTe with mercury (Hg) results in the formation of nanocrystals composed of CdHgTe. Redshifts in the absorbance / photoluminescence and enhanced PL spectra are observed with the increasing Hg content (AL Rogach, MT Harrison, SV Kershaw, A. Kornowski, MG Burt, A. Eychmüler, and H. Weller , "Colloidally Prepared CdHgTe and HgTe Quantum Dots with Strong Near-Infrared Luminescence," phys.stat.sun, 224 (1): 153-158, 2001). The alloys of Cdi-xHgxTe are popular components in devices used for the technology of near-infrared detectors. A variety of methods have been developed to create these materials. U.S. Patent No. 7,026,228-Hails et al, issued April 11, 2006, describes a process for manufacturing semiconductor devices and layers of HgCdTe in an epitaxy process in vapor organic, metal (MOVPE) with steam of mercury and volatile compounds of organoteluride and organocadmium. In a different procedure, U.S. Patent No. 7,060,243 - Bawendi et al, issued June 13, 2006, describes the synthesis of tellurium containing nanocrystals (CdTe, ZnTe, MgTe, HgTe and their alloys) by injection of organometallic precursor materials in organic solvents (TOP / TOPO) at high temperatures. U.S. Patent No. 6, 126,740-Schulz, issued October 3, 2000, describes another non-aqueous method of preparing mixed semiconductor nanoparticles from the reaction between a metal salt and the chalcogenide salt in an organic solvent in the presence of a volatile packing agent. The mixtures of CdTe and PbTe have also been investigated for IR detection in the spectral range of 3 to 5 and m. However, because these materials have such fundamentally different structures and properties (S. Movchan, F. Sizov, V. Tetyorkin. "Photosensitive Heterostructures CdTe-PbTe Prepared by Hot-Wall Technique," Semiconductor Physics, Quantum Electronics &Optoelectronics 2: 84-87, 1999. V), the preparation of the alloy is extremely difficult. U.S. Patent No. 5,448,098 - Shinohara et al, issued September 5, 1995, discloses a superconducting device based on photo-conductor ternary semiconductors such as PbCdTe or PbSnTe. The impurification of telluride quantum lines, for example CdTe, with transition metals, for example manganese, offers the possibility of combining optical and magnetic properties in a simple nanoparticle ((a) S. ackowski, T. Gurung, HE Jackson, LM Smith, G. Karczewski, and J. Kossut, "Exciton-Controlled Magnetization in Single Magnetic Quantum Dots," Appl. Phys. Lett. 87: 072502-1-072502-3, 2005. (b) T. Kümmel, G. Bacher, MK Welsch, D. Eisert, A. Forchel, B. Konig, Ch. Becker, W. Ossau, and G. Landwehr, "Semimagnetic (Cd, Mn) Te Single Quantum Dots-Technological Access and Optical Spectroscopy," J Cryst, Growth, 214/215: 150-153, 2000). Unfortunately, these materials are mainly manufactured using thin film technologies such as chemical vapor deposition or molecular beam epitaxy, and the need for a highly controlled environment during growth makes these materials inaccessible. Some mixed metal tellurides such as CdHgTe (SV Kershaw, M. Butt, M. Harrison, A. Rogach, H. Weller, and A. Eychmüller, "Colloidal CdTe / HgTe Quantum Dots with High Photoluminescence Quantum Efficiency at Room Temperature," Ap L. Phys.Lett., 75: 1694-1696, 1999); and CdMnTe (N. Y. Morgan, S. English, W. Chen, V. Chernornordik, A. Russ, P.D. Smith, A. Gandjbakhche, "Real Time In Vivo Non-Invasive Optical Imaging Using Near-Infrared Fluorescent Quantum Dots," Acad. Radiol, 12 (3): 313-323, 2005) the quantum lines have been prepared in aqueous solution, which is an adaptation of the synthetic technique described in Rajh, OL. et al. supra However, all of the aforementioned methods involve many processing steps, sophisticated equipment or large volumes of organometallic, expensive and toxic metal precursors and organic solvents. A simple tellurite reduction method for preparing cadmium telluride materials has been used using sodium tellurite (Na2TE03) as a tellurium precursor salt with a suitable reducing agent, such as NaBH4 with My + cations (H. Bao, E. Wang , and S. Dong, "One-Pot Synthesis of CdTe Nanocrytals and Shape Control of Luminescent CdTe-Cystine Nanocomposites," small, 2 (4): 476-480, 2006). Accordingly, there is a need in the art for a low cost, generalizable, environmentally friendly, "single-vessel" method of directly producing metal oxide, alloy metal, semiconductor, oxide, and other forms of nanocomposite particles that have effective functionality in a plurality of scientific disciplines.

BRIEF DESCRIPTION OF THE INVENTION In various aspects, the present invention provides methods for producing a composite nanoparticle comprising a nanoparticle confined within a collapsed, crosslinked polymeric material that is itself a nanoparticle. The term "composite nanoparticle" in this specification means a nanoparticle substantially confined within a crosslinked polymeric material. In various aspects, the present invention provides the composite nanoparticles when made by the methods of the present invention. In various aspects, the present invention provides methods for providing non-encapsulated nanoparticles from the aforementioned composite nanoparticles. In various aspects, the present invention provides methods for producing fully or partially carbon-coated nanoparticles from composite nanoparticles. In various embodiments, the present inventions teach the ability to make a wider variety of composite nanoparticles, including oxide, semiconductors, more complex composite nanoparticles. In various aspects, the present invention provides methods for producing a composite nanoparticle comprising the steps of: a) providing a polymer solution that includes a polymeric material and a solvent; b) collapsing at least a portion of polymeric material around one or more precursor portions to form a composite precursor portion having an average diameter in the range of about 1 nm to about 100 nm; c) crosslinking the polymeric material of the composite precursor portion; and d) modifying at least a portion of the precursor portions of the composite precursor portion to form one or more nanoparticles, and thereby forming a composite nanoparticle. "Confined" in this specification means that the nanoparticle is substantially within the limits of the dimensions of the collapsed polymer and includes, but is not limited to, the situation where portions of the polymer may be interacting strongly with the nanoparticle within the polymer dimensions. As used herein, the term "precursor portion" refers to a compound or entity, at least a portion of which is a component of the eventual nanoparticle formed, and includes nanoparticle precursors. A polymeric material for use in the practice of the present inventions can be any molecule capable of collapsing, containing monomer units, which can be synthetic or of natural origin and which can be linear, branched, hyperbranched or dendrimeric. Non-limiting examples of suitable polymeric materials are discussed in various examples, which include, but are not limited to, poly (diallyldimethylammonium chloride) (PDDA), and polyacrylic acid (PAA), poly (styrene sulfonic acid) ( PSS). This can also be any polymer that contains ionized or ionizable portions along its length and is of sufficient length such that the collapsed shape has nanometric dimensions. The collapsed shape can be of different morphologies, such as, for example, spherical, elongated or multi-lobed. The dimensions in any direction are anywhere from 0.1 to 100 nm, and preferably from 1 to 50 nm. A wide variety of solvents can be used to form a polymer solution for use in the present inventions. In various embodiments, the polymer solution is preferably an aqueous solution. In preferred embodiments of the present inventions, a chosen polymer is dissolved in a suitable solvent to form a solution of the polymer. The solvent may be water, an organic solvent or a mixture of two or more such solvents. The addition to the solution of the collapsing agent induces a collapse of the substantially surrounding polymer, for example, confines a precursor portion.

The collapsing agent can by itself be the precursor portion. The chosen confined agent, for example a precursor portion, can be, for example, a charged organic or inorganic ion or a combination thereof. For example, the bound agent may be an ion from an organic salt, an inorganic salt, or an inorganic salt that is soluble in water where the inorganic salt soluble in water is of the form MxAy where M is a metal cation belonging to Groups I to IV of the Periodic Table, which has a charge + y, and A is the ion opposite to M with a charge -xo or a combination thereof. The confined agent could further comprise a mixture of ions from at least two inorganic salts. The collapsing agents are usually water-soluble inorganic salts, most preferably those containing metal cations and their corresponding anions, which are known to induce a collapse transition for certain polymeric materials. The non-limiting examples are Cd (N03) 2, Zn (N03) 2, Cu (S04), Pb (N03) 2, Pb (CH3COO) 2, Ag (N03), Mn (S04), Ni (N03) 2. A wide variety of techniques can be used to collapse the polymeric material around a precursor portion. For example, in various embodiments a collapsing agent such as a different solvent, a different ionic species (eg, a salt) or combinations thereof may be used. In various embodiments, it is preferred that the precursor portion itself serve as a collapsing agent. Multiple collapse agents can be used. In various embodiments, at least one collapsing agent preferably comprises at least one ionic species. Preferably, in various embodiments, at least one ionic species is a precursor portion. In various embodiments, the precursor portion comprises at least one metal cation, complexed metal cation, or complexed metal anion. In various embodiments where the precursor portion comprises a metal cation, complexed metal cation or complexed metal anion, the modification step (production medium) comprises the treatment of the cation, the complexed cation, or the anion complexed with radiation? or an agent selected from a reducing agent or an oxidizing agent to effect the production of the nanoparticle comprising elemental metal confined within the collapsed, crosslinked polymeric material. In various embodiments, the precursor ratio comprises two or more different metals. In various embodiments where the precursor portion comprises two or more different materials, the modification step comprises the formation of an alloy of two or more of the two or more metals. In various embodiments, the precursor portion comprises ions selected from a cation, completed cations, or metal anions complexed from a plurality of metals and the modification step comprises the treatment of cations or complexed anions, with radiation, for example, radiation? , or an agent selected from a reducing agent or an oxidizing agent to effect the production of the nanoparticle comprising an alloy of said metals, confined within the collapsed, crosslinked polymeric material. In various embodiments, the precursor portion comprises a compound that contains a metal species. By the term "metal-containing compound" is meant a compound that contains a metal or metalloid in any valence state. In various embodiments of the present inventions, having an elemental metal, alloy comprising a metal, or a compound containing a metal species, the metal is preferably cadmium, zinc, copper, lead, silver, manganese, nickel, gold, magnesium , iron, mercury, platinum or a combination thereof. In various embodiments of the present inventions having a compound containing a metal species, the compound containing a metal species preferably comprises one or more of a sulfide, selenide, telluride, chloride, bromide, iodide, oxide, hydroxide, phosphate, carbonate, sulfate, chromate and a combination thereof. In various embodiments, a composite precursor portion formed by a method of the present inventions has a mean diameter in the range between about 1 nanometer (nm) to about 100 nm. In various embodiments, the composite precursor portion has an average diameter in one or more of the ranges between: (a) about 1 nm to about 10 nm; (b) about 10 nm to about 30 nm; (c) about 15 nm to about 50 nm; and (d) about 50 nm to about 100 nm). It should be understood that the term "average diameter" is not intended to imply any kind of specific symmetry (e.g., spherical, ellipsoidal, etc.) of a composite precursor portion. Rather, the composite precursor portion could be highly irregular and asymmetric. > The formation of the intramolecular covalent bonds that effect the crosslinking of the polymeric material can be induced either by chemical means or by irradiation. The chemical crosslinking means can also be carried out through the use of multi-toothed molecules as crosslinkers. These molecules contain multiple functional groups that are complementary to, and therefore, can form covalent bonds with the functional groups of the polyelectrolyte polymeric material. These molecules can be linear, branched or dendrimeric. For example, a molecule containing multiple amino groups, such as 2,2'-ethylenedioxydiethylamine, can effect intramolecular crosslinking of collapsed poly (acrylic acid). The crosslinking reaction in this case is promoted by the addition of an activating agent, typically used for the formation of the amide bond, such as a carbodiimide. The chemical crosslinking can be carried out to derivatize the polymer, such that a fraction of the ionizable groups is converted to groups that can be crosslinked through free radical reactions. An example is to convert some of the carboxylic acid groups from poly (acrylic acid) to allyl esters. The allyl groups can then be reacted to form intramolecular bonds through the radical tape. The crosslinking by irradiation can be effected by exposing a collapsed polymer solution to a source of electromagnetic radiation. The radiation source can be, for example, an excimer laser, a mercury arc lamp, a light emitting iodine, a UV germicidal radiation lamp or gamma rays.

A wide variety of techniques can be used in the present invention to modify at least a portion of the precursor portions of the composite precursor portion, to form one or more nanoparticles, and thereby form a composite nanoparticle. These techniques are also referred to as "means or means of production" in the present, since these are used in the production of the nanoparticle. Suitable techniques for modifying a precursor portion to form the desired nanoparticle include, but are not limited to, exposure to electromagnetic radiation, chemical treatment and combinations thereof. Examples of suitable exposure to electromagnetic radiation include, for example,? Radiation, ultraviolet radiation, infrared radiation, etc. In various embodiments, electromagnetic radiation is coherent radiation, such as is provided, for example, by a laser, in others it is inconsistent, such as that which is provided, for example, by a lamp. Examples of chemical treatments include, but are not limited to, contact with an oxidizing agent, contact with a reducing agent, the addition of at least one opposite ion, a compound containing the opposite ion, or a precursor for the ion. opposite, where the opposite ion is an opposite ion with respect to the precursor portion in the portion thereof. In general, modification of the precursor portion results in the formation of a nanoparticle that is no longer soluble within the solvent of the polymer solution. The reaction either by reduction or oxidation of the ions, ionic precursor portions, within the crosslinked polymeric material to form the composite nanoparticles, can be effected through chemical, electrochemical or photochemical means. The resulting nanoparticles can be, for example, semiconductor crystals, including but not limited to CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, PbS, PbSe, PbTe, Cul, HgS, HgSe, and HgTe. The nanoparticles can also be metal alloys. In various embodiments, a composite nanoparticle formed by a method of the present inventions has a mean diameter in the range of about 1 nanometer (nm) to about 100 nm. In various embodiments, the composite nanoparticle has an average diameter at one or more of the ranges between: (a) about 1 nm to about 10 nm; (b) about 10 nm to about 30 nm; (c) about 15 nm to about 50 nm; and (d) about 50 nm to about 100 nm). It should be understood that the term "average diameter" is not understood to imply any kind of specific symmetry (e.g., spherical, ellipsoidal, etc.) of a composite nanoparticle. Rather, the composite nanoparticle could be highly irregular and asymmetric. In various embodiments, the nanoparticle, formed from a precursor portion, comprises an alloy of two or more different metals. In various embodiments, where the precursor portion comprises two or more different metals, the modification step comprises the formation of an alloy of two or more of the two or more metals. In various embodiments, the nanoparticle, formed from a precursor portion, comprises a compound containing a metal species. By the term "metal-containing compound" is meant a compound that contains a metal or metalloid in any valence state. In various embodiments of the present inventions, having an elemental metal, alloy comprising a metal, or a compound containing a metal species, the metal is preferably cadmium, zinc, copper, lead, silver, manganese, nickel, gold, magnesium , iron, mercury, platinum or a combination thereof. In various embodiments of the present inventions having a compound containing a metal species, the metal-containing compound preferably comprises one or more of a sulfide, selenide, telluride, chloride, bromide, iodide, oxide, hydroxide, phosphate, carbonate , sulfate, chromate and a combination thereof. In various aspects, the present inventions provide methods for producing a nanoparticulate material, comprising the steps of: (a) providing a polymer solution comprising a polymeric material and a solvent; (b) the collapse of at least a portion of the polymeric material around one or more precursor portions to form a composite precursor portion; (c) crosslinking the polymeric material of the composite precursor portion; and (d) modifying at least a portion of precursor portions of the composite precursor portion to form one or more nanoparticles having an average diameter in the range of about 1 nm to about 100 nm, and thereby forming a composite nanoparticle; and (e) pyrolysis of the composite nanoparticle to form a nanoparticulate material. In various embodiments, the pyrolysis conditions are controlled such that the nanoparticulate material formed comprises at least one nanoparticle partially coated with carbon. In various embodiments, the present inventions provide methods for producing a metal nanoparticle, comprising the pyrolysis of the composite nanoparticle prepared by a method of the present invention described herein, wherein the metal nanoparticle is an elemental metal, an alloy comprising a metal with at least one other metal, or a compound containing a metal species, at an effective temperature to substantially remove the polymeric material. In various embodiments, the present inventions provide methods for producing a carbon-coated metal nanoparticle, comprising the incomplete pyrolysis of the composite nanoparticle, prepared by a method of the present invention described herein, wherein the metal nanoparticle is selected from an elemental metal, an alloy comprising metal with at least one other metal, and a compound containing a metal species, at a temperature to effect the production of the metal nanoparticle coated with carbon. In various aspects, the present inventions provide for composite nanoparticles, when they are made by a method or process of one of the inventions described herein. In various aspects, the present inventions provide metal nanoparticles non-confined and totally or partially coated with carbon, when they are made by methods of the present inventions described herein. Various embodiments of the present inventions can be of value in the production of semiconducting nanoparticles, including, for example, quantum lines or dots such as CdSe, CdS, CdTe and others. Various embodiments of the present invention may be of value in the production of complex salts, such as LiFeP04, and oxide particles, such as Fe203. Accordingly, in various embodiments, the precursor portion comprises at least one metal cation, complexed metal cation or complexed metal anion, and the production medium (modification step) comprises the treatment of the metal cation, the complexed cation or the anion complexed with a suitable counter ion or a precursor thereof for effecting the production of the composite nanoparticle comprising a compound containing a metal species. In various embodiments, the precursor portion comprises an anion, and the modification step (production medium) comprises treating the anion with a suitable metal counter ion or a precursor thereof, to effect the production of the composite nanoparticle, comprising a compound that contains the metallic species. In various aspects, the modification step comprises the use of a suitable counter ion or a precursor thereof to effect the production of a semiconductor nanoparticle or a composite nanoparticle. In various aspects, the modification step comprises the use of a suitable counter ion or precursor thereof to effect the production of a composite nanoparticle that includes a complex salt. In various aspects, the modification step comprises the use of a suitable counter ion or the precursor thereof to effect the production of a nanoparticle comprising a hydroxide. In a preferred aspect, the hydroxide can subsequently be heated to convert the hydroxide to an oxide. The aforementioned composite nanoparticles comprising a compound containing a metal species, a complex salt, a hydroxide, or oxide, a semiconductor entity, can be, in the various embodiments, effectively pyrolyzed to substantially remove polymeric material, or only to partially remove the polymeric material to produce, for example, a total or partially coated nanoparticle with carbon. Thus, the various embodiments of the present invention relate to the methods of making composite nanoparticles and nanoparticles that can have a wide variety of applications in a variety of sectors, including, but not limited to, biology, analytical chemistry and combinatorial, catalysis, energy and diagnosis. By using starting materials that are readily soluble in water, the present inventions, in the various embodiments, can provide nanoparticles and composite nanoparticles having unique characteristics applicable in the aforementioned sectors, whose nanoparticles can be soluble in water. The synthetic routes of the various embodiments of the present inventions include, but are not limited to, synthesis in a "single container" system in an aqueous medium. The particle size can be controlled, for example, by varying the molecular weight of the polymer, the degree of internal crosslinking, the solution conditions and the amount of aggregate collapse agent. The polymeric coating can be chosen to have desirable functional groups that can impart desirable properties, for example, that have a capacity for binding to molecules, such as proteins or to increase or decrease adhesion to substrates. In various embodiments, the present invention provides methods for making water-dispersible composite nanoparticles with inherent chemical functional groups that can be reacted with complementary functional groups on other molecules. Dispersible in water, in this context, refers to the formation of composite nanoparticles that can be prevented from aggregation in aqueous solution by adjusting the solution conditions. In various embodiments, the methods of the present invention provide a composite nanoparticle having at least one confined agent substantially surrounded by a polymeric material, which polymer can be either a linear or branched polyanion or polycation, or a combination thereof. In preferred embodiments of the present invention, a chosen polymer is dissolved in a suitable solvent to form a solution of the polymer. The solvent may be water, an organic solvent or a mixture of two or more such solvents. The addition to the collapse agent solution includes a collapse of the substantially surrounding polymer, for example, confining the agent herein. The chosen bound agent may be a charged organic or inorganic ion or a combination thereof. For example, the bound agent may be an ion from an organic salt, an inorganic salt or an inorganic salt that is soluble in water where the inorganic salt soluble in water is of the form MxAy, where M is a metal cation belonging to Groups I to IV of the Periodic Table of the elements, which has a charge + y and A is the ion opposite to M with a load -x, or a combination thereof. The confined agent could further comprise a mixture of ions from at least two inorganic salts. In various embodiments, to retain the conformation of the collapsed polymer, the crosslinking of the collapsed polymer is achieved by exposing the polymer to radiation? or UV radiation. Preferably, the UV radiation is UV laser radiation or UV arc lamp radiation. In various modalities, the intramolecular cross-links of the intra-molecular cross-linking process are chemically produced, for example, with the carbodiimide chemistry with a homobi-functional cross-linker. A preferred embodiment of the present invention involves the formation of nanoparticles composed by the addition of ions that induce the formation of precipitates of the bound agent within the collapsed polymeric material, wherein the collapsed polymer is intra-molecularly cross-linked. As used in the present "precipitation" of a confined ion it refers to the modification of the ion for a compound that is substantially insoluble in the solvent of the polymer solution. Various preferred embodiments of aspects of the present invention include, but are not limited to, the use of polymers dissolved in a solvent, usually water, to make a dilute solution. Polymers with ionizable groups, for example, NH2, RNH, and COOH can be chosen because of their solubility in water under appropriate solution conditions and their ability to undergo a collapse transition when exposed to certain concentrations of ions in solution, usually through the addition of an inorganic salt. The collapse of the polymer causes the confinement of some of the ions within a collapsed polymer structure. In order to make permanent the collapsed conformation of polymers, the formation of intramolecular bonds is facilitated either through the exposure of radiation, through the use of chemical crosslinkers or both. In various embodiments, the collapsed intramolecular crosslinked polymer has some of the ions from an inorganic salt confined within the collapsed structure as the basis for the formation of the composite nanoparticle. The confined ions, for example, can be reduced, oxidized and / or reacted (for example, by precipitation with an external agent), which results in the formation of the nanoparticle composed of the inner nanoparticle confined within the intramolecular, cross-linked polymer material. , collapsed. Unreacted ionizable groups, for example, can serve as future sites for subsequent chemical modification, dictate the solubility of the particles in different media, or both. An ionizable portion or group is any chemical functional group that can be charged by adjusting the solution conditions, while the ionized portions refer to the chemical functional groups that are loaded regardless of the solution conditions. The ionized or ionizable portion or group can be either cationic or anionic and can be continuous along a complete chain as in the case of regular polymers, or it can be interrupted by blocks containing different functional groups, as in the case of the block polymers. In various embodiments, a preferred cationic group is the amino group and the preferred anionic groups are carboxylic acid, sulfonic acid, phosphates and the like. For cationic polymers, examples are poly (allylamine), poly (ethylene imine) poly (diallyldimethylammonium chloride), and poly (lysine). For the anionic polymers, the examples are poly (acrylic acid), poly (styrene sulfonic acid), poly (glutamic acid), etc. The block polymers are made up of polymer blocks having different functional groups. The block polymers can be made up of blocks of any of the mentioned anionic and cationic polymers and another polymer that imparts a specific desirable property to the block polymer. In various embodiments, the functional groups of the polymeric material can be used to conjugate the composite nanoparticles to other molecules that contain complementary functional groups. These molecules can be any member of the affinity binding pairs, such as antigen-antibody, DNA-protein, DNA-DNA, DNA-N, biotin, avidin, hapten-antihapten, protein-protein, enzyme-substrate and combinations thereof. These molecules can also be protein, ligand oligonucleotide, aptamer, carbohydrate, lipid or other nanoparticles. An example is the conjugation of the encapsulated nanoparticles with poly (acrylic acid) to the proteins through the formation of amide bonds between the amine groups on the proteins and the carboxylic acid groups on the polyacrylic acid (PAA). A fraction of the functional groups of the polyelectrolyte polymer can also be modified to convert them to other functional groups that can be used for conjugation. For example, a bifunctional hetero molecule containing an amine group and a latent thiol group can be reacted with the nanoparticles wrapped with the poly (acrylic acid) through the formation of the amide bond, thereby converting the carboxylic acid to a thiol group. The thiol group can be used for conjugation to other molecules containing thiol-reactive groups. The wide variety of potential applications for composite nanoparticles and nanoparticles, produced by the methods of the present invention include, but are not limited to, the absorption of light energy selected from the group consisting of UV, visible light and IR light, in where the composite nanoparticle or the nanoparticle are used as pigments or are incorporated into an optical device. In various modalities, after absorption of the light energy, the composite nanoparticle may be able to emit light. In various embodiments of the present invention, methods are provided wherein the polymeric material is conjugated to molecules containing functional groups for binding to complementary binding partners, to form an affinity bond pair selected from the group having an enzyme pair -substrate, antigen-antibody, DNA-DNA, DNA-RNA, biotin-avidin, hapten-antihapten and combinations thereof. Preferably, the molecules are selected from the group consisting of protein, ligand, oligonucleotide, aptamer and other nanoparticles. In various embodiments, a composite nanoparticle of the present invention can be used, for example, to improve spectroscopic techniques, including vibrational spectroscopy. In various embodiments, methods are provided where the composite nanoparticles are further assembled on a surface of a substrate using the assembly layer by layer or additionally aggregated into three-dimensional systems of composite nanoparticles, whereby three-dimensional systems are created on a surface. In various modalities, this substrate is a film. Accordingly, in various aspects the present invention provides a coated substrate having a plurality of layers of composite nanoparticles as described herein, sandwiched between adjacent layers of oppositely charged compounds. In various embodiments, a coated substrate as described herein, is preferably coated, with a nanoparticle composed of CdS / PAA and the oppositely charged compound is poly (allylamine) hydrochloride (PAH). In various embodiments, the present invention provides the use of a composite nanoparticle as described herein, in the production of a multilayer coated substrate. This substrate could be of value, for example, as one more of: (a) a solid substrate comprising catalytic or otherwise reactive nanoparticles; and (b) an optical filter or as an element in an optical device where the incorporated composite nanoparticles have useful properties.ic.

In various embodiments, the compounds according to the present invention could be of value as semiconductor materials, for example, as quantum dots.

BRIEF DESCRIPTION OF THE FIGURES The foregoing and other aspects, modalities, objectives, characteristics and advantages of the present invention can be more fully understood from the following description, in conjunction with the appended figures. In the figures, similar reference characters generally refer to similar characteristics and similar structural elements throughout the various figures. The figures are not necessarily to scale, rather emphasis is placed on the illustration of the principles of the present invention, wherein: Figure 1 depicts the UV-Vis absorption spectra of the composite CdS / PAA nanoparticles prepared in accordance to Example 13; Figure 2 represents the emission spectra of different nanoparticles composed of CdS / PAA prepared according to Example 13; Figure 3 represents a STEM image of nanoparticles composed of CdS / PAA prepared according to Example 13; Figure 4 represents the UV-Vis absorption and emission spectra of the CdSe / PAA compound nanoparticles prepared according to Example 14; Figure 5 represents the absorption of uv-Vis and the emission spectra of the nanoparticles composed of (CdSe-CdS) / PAA prepared according to Example 15; Figure 6 represents the absorption of uv-vis and the emission spectra of the nanoparticles composed of CdTe / PAA prepared according to Example 16; Figure 7 represents the absorption of uv-vis and emission spectra of the nanoparticles composed of (CdTe-ZnS) / PAA produced according to Example 17; Figures 8a-8c depict STEM with EDX analysis of the nanoparticles composed of LiFeP04 / PAA produced according to example 18; Figure 9 depicts an XRD pattern of the nanoparticles composed of LiFeP04 / PAA produced according to Example 18; Figures 10a-10c depict STEM with EDX analysis of the nanoparticles composed of Fe203 / PAA produced according to Example 19; Figure 11 depicts an XRD X-ray diffraction pattern of the Fe203 / PAA compound nanoparticles produced according to Example 19; Figure 12 represents a STEM image of the ZnO / PAA nanoparticles made according to Example 20; Figure 13 represents the uv-vis absorbance and emission spectra of the ZnO / PAA compound nanoparticles made according to Example 20; Figure 14 depicts the emission spectra of the coated CdS / PAA composite nanoparticles and the uncoated polystyrene prepared according to Example 21; Figure 15 represents the uv-vis absorption spectra of the Ag / PAA compound nanoparticles produced according to Example 22; Figure 16 represents a STEM image of the Ag / PAA compound nanoparticles produced according to Example 22; Figure 17 represents the uv-vis absorption spectra of the Au / PAA composite nanoparticles produced according to Example 23; Figure 18 represents the STEM image of the Au / PAA composite nanoparticles produced according to Example 23; Figure 19 represents the uv-vis spectra of the nanoparticles composed of (Au, Ag) / PAA produced according to Example 24; Figures 20a-20c depict STEM with the EDX analysis image of the nanoparticles composed of (Au, Ag) / PAA produced according to Example 24; Figure 21 represents the uv-vis and emission spectra of the CdS / PSS compound nanoparticles produced according to Example 27; Figure 22 represents the uv-vis and emission spectra of the CdS / PDDA composite nanoparticles produced according to Example 28; and Figure 23 represents the absorbance and emission spectra of the CdPbTe / PAA nanoparticles produced according to Example 36 according to the present invention; Figure 24 represents the absorbance and emission spectra of the nanoparticles composed of CdZnTe / PAA produced according to Example 37 according to the invention; and Figure 25 represents the absorbance and emission spectra of the CdMnTe / PAA nanoparticles produced according to Example 38 according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION EXAMPLES In the following examples, the term: (a) My + / polymer refers to the polymeric material collapsed with the metallic cation MY +, where M is the metal established in the example; and (b) Ax ~ / polymer refers to the collapsed polymeric material, which is collapsed with the anion Ax ~. In the case of multiple cations or anions used to collapse a simple polymer, the different metal cations and anions will be separated by a comma "," in the case of (Miyl +, M2y2, etc.) / polymer and (Aixl ~, A2x2 ~ , etc ...) / Polymer (for example Cd2 / PAA, C1 ~ / PDDA, etc.). The nanoparticles formed from metal ions will be designated as Mlxi Aiyi / Polymer (for example CdS / PAA, (CdS, PbS) / PAA, etc.). The nanoparticles formed from the metal ions that have been treated with another agent to form a different material will be designated by a "-" as in (lxlAiyi-M2y2A2y2) / Polymer (for example (CdSe-CdS) / PAA, (CdTe -ZnS) / PAA, etc.).

Example 1: Polycation collapse with anion (-1) In a 400 ml plastic container, 3.0 ml of poly (dialdimethylammonium chloride) (PDDA) [Sigma, average molecular weight 400-500K, 20% in water were diluted ] to 300 ml with deionized water. The solution was stirred for 10 minutes. Aliquots of 5 ml were obtained and placed in 20 ml scintillation bottles. To each were added dropwise with vigorous stirring 5 ml of aqueous solutions of sodium chloride of different concentrations (2 mM-60 mM) yielding 10 ml of the Cl '/ PDDA solutions with different [Cl ~] between 1 and 50 mM and a final PDDA concentration of 1 mg / ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of the concentration of sodium chloride suddenly changed to approximately 10 mM; this was taken as the point of collapse of PDDA with Cl ", such that at lower concentrations, the PDDA is mainly in an extended configuration.

Example 2: Polycation collapse with anion (-2) In a 400 ml plastic container, 3.0 ml of poly (dialdimethylammonium chloride) (PDDA) [Sigma, average molecular weight 400-500K, 20% in water were diluted ] to 300 ml with deionized water. The solution was stirred for 10 minutes. Aliquots of 5 ml were obtained and placed in 20 ml scintillation bottles. To each were added dropwise with vigorous stirring 5 ml of aqueous solutions of Na 2 SO of different concentrations (2 mM-20 mM) yielding 10 ml of the solutions of S042"/ PDDA with different [S042 ~] between 1 and 10 mM and a final PDDA concentration of 1 mg / ml.The relative viscosity of each solution was measured with an Ostwald viscometer.The viscosity as a function of the concentration of sodium chloride suddenly changed to approximately 3 mM, this was taken as the point of collapse of PDDA with S042 ~, such that at lower concentrations, the PDDA is mainly in an extended configuration.

Example 3: Polycation collapse with anion (-3) In a 400 ml plastic container, 15 ml of poly (dialdimethylammonium chloride) (PDDA) [Sigma, average molecular weight 400-500K, 20% in water was diluted ] to 300 ml with deionized water. The solution was stirred for 10 minutes. Aliquots of 5 ml were obtained and placed in 20 ml scintillation bottles. To each were added dropwise with vigorous stirring 5 ml of aqueous solutions of Na3P04 of different concentrations (2 mM-50 mM) producing 10 ml of the solutions of P03 ~ / PDDA with different [P043 ~] between 1 and 25 mM and a final PDDA concentration of 5 mg / ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of the concentration of sodium chloride suddenly changed to approximately 2 mM; this was taken as the point of collapse of PDDA with P043 ~, such that at lower concentrations, the PDDA is mainly in an extended configuration.

Example 4: Collapse of the polyanion with the cation (+1) In a 400 ml plastic container, 400 mg of (PAA) (Sigma, average molecular weight Mv 1.2 million) was dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. PH measurements were performed using a narrow-range pH paper. Aliquots of 5 ml of PAA were obtained with adjusted pH, and aliquots of 5 ml were added to each one, and placed in 20 ml scintillation flasks. To each was added dropwise with vigorous stirring 5 ml of aqueous solutions of sodium chloride of different concentrations (0.2 mM-10.0 mM) yielding 10 ml of Na PDDA solutions with different [Na +] between 0.1 mM and 5.0 mM and a final PAA concentration of 1 mg / ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of the concentration of sodium chloride suddenly changed to approximately 2 mM; this was taken as the point of collapse of PAA with Na +, such that at lower concentrations, the PAA is mainly in an extended configuration.

Example 5: Collapse of the polyanion with the cation (+2) In a 400 ml plastic container, 400 mg of (PAA) (Sigma, average molecular weight Mv 1.2 million) was dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. PH measurements were performed using a narrow-range pH paper. Aliquots of 5 ml of PAA were obtained with adjusted pH, and aliquots of 5 ml were added to each one, and placed in 20 ml scintillation flasks. To each was added dropwise with vigorous stirring 5 ml of aqueous solutions of Cd (N03) 2 of different concentrations (0.1 mM-6.0 mM) producing 10 ml of Cd2 + / PDDA solutions with different [Cd2 +] between 0.1 mM and 3.0 mM and a final PAA concentration of 1 mg / ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of the concentration of Cd (N03) 2 changed suddenly to between 1-2 mM; this was taken as the point of collapse of PAA with Cd2 +, such that at lower concentrations, the PAA is mainly in an extended configuration. The addition of more Cd (N03) 2 such that the final concentration > 2 mM caused a white precipitate to form. Solutions with a final concentration of 1.2 mM Cd (N03) 2 and approximately 0.7 mg / ml PAA were then prepared for use in the subsequent examples below; This solution is called Cd2 + / PAA in this work.

Example 6: Collaion of the polyanion with the cation (+3) In a 400 ml plastic container, 400 mg of poly (Tylenol phonic acid) (PSS) (Alfa Aesar, average molecular weight of 1 million) was dissolved in 200 My deionized water. 5 ml aliquots were obtained from the PSS solution, and placed in 20 ml scintillation flasks. To each was added dropwise with vigorous stirring, 5 ml of the aqueous solutions containing FeCl 3 of different concentrations (0.2 m -20.0 mM) producing 10 ml of the Fe3 * / PDDA solutions with different [Fe3] between 0.1 mM and 10.0 mM and a final PSS concentration of 1 mg / ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of the concentration of FeCl3 suddenly changed to approximately 2 mM; this was taken as the point of collapse of PSS with Fe3 +, such that at lower concentrations, the PSS is mainly in an extended configuration.

Example 7: Polyanion collapse with 2 cations In a 400 ml plastic container, 400 mg of PAA (Sigma, average molecular weight 1.2 million) was dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and vigorously stirred for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were performed using a narrow-range pH paper. Aliquots of 5 ml were obtained and placed in 20 ml scintillation flasks. To each was added dropwise with vigorous stirring, 5.0 ml of the aqueous solutions containing FeCl2 and LiCl at a molar ratio of (2: 1) of different concentrations * (0.2 mM - 8.0 mM) yielding 10 ml of the solutions of (2Fe2 +, Li +) / PAA with different [2Fe2 +, Li2 +] between 0.1 mM and 4.0 mM and a final PAA concentration of 1 mg / ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The speed as a function of the concentration of FeCl2 and LiCl suddenly changed to approximately 0.3 mM; this was taken as the point of collapse of PAA with two 2Fe2 +, Li + such that at lower concentrations, the PAA is mainly in an extended configuration.

* Concentrations refer to the total concentration of both combined metal ions.

Example 8: Preparation of Cd2 + / PAA crosslinked composite nanoparticles, according to the invention using mercury arc lamp A Cd2 + / PAA solution was prepared by the dropwise addition of 10 ml of a solution of Cd (N03) 2 0.005 M to 10 ml of an aqueous solution of 2 mg / ml of PAA (Sigma, M "average 1.2 million PAA, pH adjusted to 6.8 with 0.1 M sodium hydroxide). The solution was exposed to light from a 200W mercury arc lamp for about 1 hour to effect collapse, while undergoing vigorous agitation. The irradiated solution was then dialyzed against deionized water for 3 hours. It is expected that the dialysis substantially reduces the concentration of the ions in solution, thereby reversing the collapse of the polymer. However, it was found that the viscosity of the solution remains unchanged (still low), indicating that the collapsed configuration is conserved, and that the collapsed polymer has been crosslinked to remain in the collapsed configuration. An aliquot of the solution was emptied onto mica and allowed to air dry. Imaging by atomic force microscopy indicated the presence of particles of size 10-25 nm.

Example 9: Preparation of crosslinked composite nanoparticles of Zn24 / PAA and Cd2 + / TPAA according to the invention using laser irradiation A Cd2 + / PAA solution was prepared by the dropwise addition of 10 ml of a solution of Cd (N03) 2 0.005 M to 10 ml of an aqueous solution of 2 mg / ml of PAA (Sigma, IYL, average 1.2 million PAA, pH adjusted to 6.8 with 0.1 M sodium hydroxide) with vigorous stirring. The solution was exposed to 5000 pulses from an eximer laser source (10 mJ / cm3) while undergoing vigorous agitation. The laser irradiated solution was then dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. The viscosity of the solution remained unchanged by dialysis, indicating that the collapsed configuration is retained. A solution of Cd2 + / PAA was prepared by the dropwise addition of 10 ml of a solution of Cd (N03) 2 0.005 M to 10 ml of an aqueous solution of 2 mg / ml of PAA (Sigma, Mw average 1.2 million PAA, pH adjusted to 6.8 with sodium hydroxide 0.1 M) The solution was exposed to 5000 pulses from an eximer laser source (10 mJ / cm3) while undergoing vigorous agitation. The laser irradiated solution was then dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. The viscosity of the solution remained unchanged by dialysis, indicating that the collapsed configuration is retained.

Example 10: Preparation of Zn2 + / PAA crosslinked composite nanoparticles according to the invention using chemical crosslinking agents The Zn2 + / PAA solution was prepared according to Example 9. 2.0 ml of Zn2 + / PAA was placed in a glass flask of 5 mi and 160 μ? of a solution that was 26.4mg / ml in l-ethyl-N '(3-dimethylaminopropyl) carbodiimide (EDC) and 33.45mM in 2,2'- (ethylenedioxy) bis- (ethylamine) (EDE) was added under stirring constant. The resulting solution was stirred for 12 hours and then dialyzed against deionized water for 3 hours, changing the deionized water tank every hour. The Zn2 + / PAA that was not treated with the EDC / EDE solution was also dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. After dialysis, the viscosity of the Zn2 + / PAA solution treated with EDC / EDE was much lower than that of an untreated Zn2 + / PAA solution. This indicates that the collapsed configuration is retained after Zn2 + / PAA was treated with the EDC / EDE solution.

Example 11: Crosslinking of polyacrylic acid with gamma radiation to produce nanoparticles composed of Cd2 + / PAA according to the invention. 20 ml of Cd2 + / PAA, prepared as described in Example 5, were placed in a 20 ml scintillation flask. To that 200 μ? of isopropanol (ACS grade). The vial was sealed with a rubber stopper and vortexed for 10 seconds. The solution was exposed to a total dose of ~ 15 kGy of gamma radiation at a dose rate of 3.3 kGy / hour. The irradiation solution was then dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. Similarly, Cd2 + / PAA that was not exposed to gamma radiation was also dialyzed in a similar manner. After dialysis, the viscosity of the dialyzed, irradiated, collapsed solution was much lower than that of a non-irradiated, collapsed solution. Na + / PAA prepared according to Example 4, [Na +] = 2 mM, was also exposed to the same dose of gamma radiation, and similarly the viscosity of the dialyzed, irradiated NaVPAA solution was much lower than that of a solution not irradiated, collapsed.

Example 12: Crosslinking of polyacrylic acid with 4 germicidal lamps of G25T8 to produce nanoparticles composed of Cd2 + / PAA according to the invention. 20 ml of Cd + / PAA were prepared according to Example 5 and placed in a 50.0 ml glass vessel. The solution was exposed to 4 Germicidal UV lamps G25T8 (the approximate energy is 12 W / mm2) for approximately 1.5-2 hours under vigorous agitation. The irradiated solution was then dialysed against deionized water for 3 hours, changing the deionized water reservoir every hour. Cd2 + / PAA that was not exposed to the UV lamp was also dialyzed in a similar manner. The viscosity of the dialyzed Cd2 + / PAA solution, irradiated, was much lower than that of a Cd2 + / PAA solution that was not exposed to the UV lamp. PAA collapsed with Zn (N03) 2, Pb (N03) 2, Cd / Pb (N03) 2, Zn / Cd (N03) 2, FeCl2, LiCl, FeCl3, Co (S04 '), Cu (S04), Mn ( S04), Ni (CH3COOH), Zn (N03) 2 / MgCl2 was also irradiated with UV in a similar manner, and the viscosity of the dialysed, irradiated, collapsed solutions were much lower than those of a non-irradiated, collapsed solution . These solutions were filterable using a 0.2 μp nylon syringe filter.

Example 13: Composite Nanoparticles of CdS / PAA according to the invention. 20 ml of the crosslinked Cd2 + / PAA composite nanoparticles were prepared according to Example 12 and placed in a 50 ml glass vessel. Under vigorous stirring, 20.0 ml of a 0.60 mM Na2S solution was added dropwise at a rate of 2 ml / min using a syringe pump. The resulting solution was yellow. The absorbance and emission spectra of the resulting solution are shown in Figure 1. The maximum emission wavelength can be tuned to different frequencies by varying the ratio of Na2S to the amount of Cd2 + ions present in the Cd2 + solution / PAA. This is shown in Figure 2. A redshift in the Max emission is observed as more Na2S is added. Electron microscopy images of CdS / PAA scanning transmission were prepared as shown in Figure 3.

Example 14: Nanoparticles composed of CdSe / PAA according to the invention. 300 ml of Cd2 + / PAA were prepared according to Example 5. The pH of the solution was adjusted to ~ 8.5-9.0 with 0.1 M sodium hydroxide and bubbled with N2 (g) for 30 minutes in a round bottom flask of 500 mi 18.2 mg of 1, 1 '-dimethylseleourea was dissolved in 5 ml of deionized, degassed water, and sealed with a septum in a 5 ml glass flask. Using a 5 ml syringe, 4.1 ml of this solution of dimethyl selenourea was added to the Cd2 + / PAA under a nitrogen atmosphere. The resulting solution was stirred for 10 minutes and then heated on a stirring mantle at a temperature of about 80 ° C for 1 hour. After one hour, the solution was allowed to cool. The resulting solution has an absorption and emission spectrum shown in Figure 4.

Example 15: Nanoparticles composed of (CdSe-CdS) / PAA according to the invention. 150 ml of CdSe / PAA nanoparticles produced according to Example 14 were placed in a 250 ml round bottom flask. 125.0 ml of 0.30 M thioacetamide in water was added to the flask containing the CdSe / PAA nanoparticles. The resulting mixture was stirred vigorously for 5 minutes, and then heated to 802C on a heating mantle with very light stirring for 24 hours. The absorption emission spectra of the composite nanoparticles resulting from (CdSe-CdS) / PAA are shown in Figure 5.

Example 16: Composite nanoparticles of CdTe / PAA according to the invention. Under ambient conditions, 300 ml of Cd2 + / PAA produced according to Example 5 were placed in a 500 ml round bottom flask. To this solution, 0.156 g of NaBH4 and 0.312 g of trisodium citrate were added while the solution was being stirred. Immediately after the addition of borohydride and citrate, 12.5 ml of 0.01 M NaTe03 were added. After the addition of the NaTe03 solution, the solution develops a yellow color. The solution was then heated to reflux for approximately 20 hours to allow the CdTe / PAA nanoparticles to form. The spectra of absorption and emission of the resulting solution after 20 hours of reflux are shown in Figure 6.

Example 17: Nanoparticles composed of (CdTe-ZnS) / PAA according to the invention. In a 50 ml falcon tube, 1.7 ml of 3M sodium chloride was added to 15 ml of CdTe / PAA nanoparticles formed according to Example 16. The resulting mixture was vortexed for 10 seconds after which 30 minutes were added. My absolute ethanol was centrifuged at 8500 rpm for 15 minutes. After centrifugation, the brown pellet formed at the bottom of the falcon tube was rinsed with 20 ml of 70% ethanol. The resulting solution was centrifuged at 8500 rpm for 10 minutes. The brown pellet was isolated and resuspended in 15 ml of deionized water. To 10 ml of the resuspended CdTe / PAA nanoparticles, 278 L of 24 mM Zn (N03) 2 were added. The solution was stirred for 10 minutes, after which 167 pL of 39.5 mM Na2S was added. After 10 minutes of agitation, a second portion of 278 pL of 24 mM Zn (N03) 2 was added. The solution was stirred for 10 minutes, after which 167 pL of 39.5 mM Na2S was added. After a further 10 minutes of stirring, a third portion of 278 pL of 24 mM Zn (N03) 2 was added. The solution was stirred for 10 minutes, after which 167 yL of 39.5 mM Na2S were added. The solution was left in a 50 ml falcon tube for at least 3 days before taking the emission spectra. The absorption and emission spectra of the resulting solution, after 3 days, are shown in Figure 7.

Example 18: Formation of the composite nanoparticles of LiFeP04 / PAA according to the invention. A solution of 20 ml of (Fe2 +, Li +) / PAA was prepared according to Example 7 with some modifications. In summary, in a 400 ml plastic container, 400.0 mg of PAA (Sigma, average Mv of 1.2 million) was dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution was cooled to room temperature, pH was adjusted to 3.0 using 0.1 M HN03. pH measurements were performed using narrow-range pH paper. 10.0 ml of this PAA solution were taken and placed in a 50 ml glass vessel to which 10.0 ml of a solution that was 6.7 mM in FeCl2 and LiCl with vigorous stirring were added dropwise. The solution was reticulated for 1.5 hours under 4 germicidal G25T8 lamps. Then 5.0 ml of 13 mM NH4H2P04 was added to the solution of (Fe2 +, Li +) / PAA exposed to UV light. The solvent (water) of the resulting solution was removed using a rotary evaporator. When all the solvent was removed, a light green residue remained and was then dried in vacuum for 12 hours. This light green residue was placed in a tubular furnace and heated under an N2 atmosphere for 12 hours at 600BC. After 12 hours of heating in the oven, the light green residue turned black. The STEM images with the EDX analysis of the composite nanoparticles of LiFeP04 / PAA are shown in Figures 8a-8c. Figure 8a is a STEM image of LiFeP04 / PAA prepared according to the present invention, and wherein Figure 8b shows the cross-sectional abundance of phosphorus along the line explored in Figure 8a acquired using dispersive x-rays of electrons; and Figure 8c shows the cross-sectional abundance of the iron along the line explored in Figure 8a acquired using electron dispersive x-rays. The XRD pattern for the composite nanoparticles of LíFeP04 / PAA is shown in Figure 9.

Example 19: Formation of nanoparticles composed of Fe203 / PAA according to the invention. Fe203 / PAA is formed following exactly Example 17 with only one modification. The pH of the PAA should be adjusted to pH 6.8 instead of pH 3.0 using 0.1 M sodium hydroxide before adding the solution of FeCl2 and LiCl. The rest of the procedure remains the same. Surprisingly, this simple modification leads to the formation of Fe203 / PAA instead of LiFeP04 / PAA. STEM images with EDX analysis of the nanocomposite LiFeP04 / PAA particles are shown in Figures 10a-10c. Figure 10a is a STEM image of the Fe203 / PAA nanocomposite prepared according to the present invention, and wherein Figure 10b shows the cross-sectional abundance of the iron along the line explored in Figure 10a, acquired using lightning x electron dispersants; and Figure 10c shows the cross-sectional abundance of the phosphor along the line explored in Figure 10a acquired using electron dispersive x-rays. The pattern of XRD is shown in Figure 11, where H is hematite, alpha-Fe203 and M is the defective spinal structure of magnetite, gamma-Fe203, maghemite. Note that although the EDX images show the presence of phosphate, the XRD pattern suggests that Fe203 is present and not LiFeP04.

Example 20: Formation of ZnO / PAA compound nanoparticles according to the invention. A 20 ml solution of Zn2 + / PAA was prepared by the dropwise addition of 10 ml of a 0.005 M Zn (N03) 2 solution to 10 ml of an aqueous solution at 2 mg / ml PAA (Sigma, average Mw 1.2 million PAA, pH adjusted to 6.8 with 0.1 M sodium hydroxide) with vigorous stirring. The solution was exposed to UV radiation for 1.5 hours under 4 germicidal G25T8 lamps as in Example 12. The pH of Zn2 + / PAA exposed to UV was adjusted to pH 11.0 with 0.1 M sodium hydroxide, and then heated to reflux by 1 hour. After reflux, the solution became slightly cloudy. The absorbance and emission spectra and the STEM image are shown in Figure 12, and the absorbance and emission spectra are shown in Figure 13.

Example 21: Incorporation of CdS / PAA compound nanoparticles according to the invention into thin films layer by layer. Polystyrene substrates were sonicated in 0.01 M sodium dodecyl sulfate + 0.1 M HCl solution for 3 minutes, rinsed with distilled water, and dried with nitrogen. Thin films were formed layer by layer (LbL) by immersing the substrate in 1 mg / ml of PAH (poly (allylamine) hydrochloride) in 0.1 M sodium chloride for 5 minutes, followed by a 5 minute rinse in sodium chloride 0.1 M, then immersed in a solution of CdS / PAA nanoparticles (prepared according to Example 13) for 5 minutes, then rinsed in 0.1 M sodium chloride solution for 5 minutes. This process was repeated 100 times. The emission spectra of the polystyrene substrate coated with thin LbL films of the composed nanoparticles of PAH: CdS / PAA are shown in Figure 14.

Example 22: Composite Ag / PAA nanoparticles according to the invention. 20 ml of Ag + / PAA were prepared according to Example 4. In summary, in a 400 ml plastic container, 400.0 mg of PAA (Sigma, average Mv of 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were made using narrow-range pH paper. 10.0 ml of this PAA solution were placed in a 20 ml scintillation flask and 10 ml of 4.0 mM AgN03 solution was added dropwise with constant agitation. 0.5 ml of 2-propanol was added to the mixture. The final solution volume of 20 ml. The bottles were sealed with rubber stoppers and subjected to 60Co irradiation using a gamma cell type G.C.220 with a dose rate of 3.3 kGy / hour, at a total dose of 15 kGy. The UV-vis spectra and the STEM images of the resulting Ag / PAA nanoparticles are shown in Figures 15 and 16, respectively.

Example 23: Au / PAA compound nanoparticles according to the invention. 20 ml of Au3 + / PAA were prepared according to Example 4. In summary, in a 400 ml plastic container, 400.0 mg of PAA (Sigma, average Mv of 1.2 million) was dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were performed using narrow-range pH paper. 10.0 ml of this PAA solution were placed in a 20 ml scintillation flask, to this 10 ml of 4.0 mM HauCl3 was added dropwise under constant agitation. 0.5 ml of 2-propanol was added to the mixture. The final solution volume was 20 ml. The bottles were sealed with rubber stoppers and subjected to irradiation with 60Co using a gamma cell type G.C. 220 with a dose rate of 3.3 kGy / hour, at a total dose of 15 kGy. The UV-vis spectra and the STE images of the resulting Au / PAA composite nanoparticles are shown in Figures 17 and 18, respectively.

Example 24: Composite nanoparticles of Au, Ag / PAA according to the invention. 20 ml of (Ag +, Au3 + / PAA according to Example 4 were prepared. In summary, 400.0 mg of PAA (Sigma, average Mv of 1.2 million) was dissolved in 200 ml of deionized water in a 400 ml plastic container. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved, once the solution had cooled to At room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide pH measurements were made using narrow-range pH paper, 10.0 ml of this PAA solution were placed in a 20 ml scintillation vial, to this one 5 ml of 4.0 mM HauCl3 was added dropwise under constant stirring, followed by the dropwise addition of 5.0 ml of Ag (N03) 4 M, and finally the addition of 0.5 ml of 2-propanol. final solution was 20 mi.The solution was exposed to 4 lamp G25T8 germicidal UV lamps (energy of approximately 12 / mm) for approximately 1.5-2 hours under vigorous agitation. After irradiation, the solution changed from colorless to light purple. The UV-vis spectra and the STEM images of the composite nanoparticles resulting from (Au.Ag) / PAA are shown in Figures 19 and 20a-20c, respectively. Figure 20a is a STEM image nanocomposite of (Au, Ag) / PAA prepared according to the present invention; and wherein Figure 20b shows the cross-sectional abundance of the silver along the line explored in Figure 20a acquired using electron dispersive x-rays; and Figure 20c shows the. Gold cross-sectional abundance along the line explored in Figure 20a, acquired using electron dispersive x-rays.

Example 25: Formation of the CdSePAA-fluorescein conjugate according to the invention. In a 1.5 ml microcentrifuge tube, 400 pL of CdSePAA (~ 0.2 mg / ml in ddH20) were combined with 4.9 mg of 1-ethyl-3- (3-dimethyl-ylaminopropyl-1) -carbodi-imide (EDC) and mg of N-hydroxysuccinimide (NHS) in 500 pL of ddH20. 100 pL of 250 mM 2-morpholinoethane sulfonic acid (MES) (pH ~ 6.5) was added. And finally, 20 yL of 5 mg / mL of fluorescein in N, N-dimethylformamide (DMF) were also added. The tube containing this mixture was wrapped in aluminum foil and placed on the rotating table for ~ 20 hours at room temperature. The resulting mixture was placed in a dialysis bag of MWCO of 10 kDa and dialyzed against ddH20. The dialysis solution (~ a dilution of 200 times each time) was changed five times in a period of ~ 24 hours. The solution remaining in the dialysis bag was recovered and centrifuged for 10 minutes at 15 minutes., 000 RCF. A brown pellet was found after centrifugation. The fluorescent supernatant was transferred to a new microcentrifuge tube and lightly purified by precipitation with the addition of ~ 1/10 volume of 3M sodium acetate (pH ~ 5.5) and a 2X volume of absolute ethanol. The resulting fluorescent precipitate was then isolated by centrifugation for 10 minutes at 15,000 RCF and resuspended in 200 μL of ddH20. The presence of the fluorescein conjugated to CdSePAA was confirmed by gel permeation chromatography using a fluorescence detector (excitation at 480 nm and emission at 515 nm).

Example 26: Formation of the CdSePAA-BSA conjugate according to the invention. In a 1.5 ml microcentrifuge tube, 900 pL of CdSe / PAA (~ 0.2 mg / mL in ddH20) were combined with 5.3 mg of EDC and 10.8 mg of NHS in 100 pL of 250 mM MES (pH ~ 6.5). And finally, 5.1 mg of bovine serum albumin (BSA) was added. The tube containing this mixture was placed on a rotary table for ~ 19 hours at room temperature. The resulting mixture was centrifuged for 10 minutes at 15,000 RCF. ~ 500 pL of the supernatant were transferred to a 100 kDa MWCO centrifuge filter and centrifuged for 12 minutes at 14,000 RCF. The resulting filtrate was discarded, and the retentate was resuspended in 500 pL of ddH20 in the same filter and centrifuged again. This was repeated three more times. The final retention was recovered for the characterization. Removal of the unconjugated BSA using the 100 kDa MWCO filter was confirmed by gel permeation chromatography. And the presence of BSA conjugated to CdSe / PAA remaining in the content was confirmed by the assay with the BioRad protein reagent.

Example 27: Composite Nanoparticles of CdS / PSS according to the invention. 400 mg of the sodium salt of Poly (styrenesulfonic acid) (Alfa Aesar, Mw average of 1 million) was dissolved in 200.0 ml of deionized water. 20.0 ml of this solution was placed in a 80 ml flask and 20.0 ml of a 4.8 mM Cd (N03) 2 solution were dropwise added thereto with vigorous stirring. The solution was exposed to germicidal UV lamps G25T8 (the approximate UV energy is 12 W / mm2) for 1 hour under vigorous agitation. Low CdS was formed by the addition of 0.5 ml of 1.4 mM Na2S to 0.5 ml of the irradiated Cd2 + / PSS solution. The absorbance and UV-visible emission spectra are shown in Figure 21.

Example 28: CdS / PDDA nanoparticles. 15.0 ml of poly (diallyldimethylammonium chloride) (PDDA) [Sigma, Mw average 400-500K, 20% by weight of water] was diluted to 300 ml with deionized water. The solution was stirred for 10 minutes. 5.0 ml of this solution were diluted to 25.0 ml with deionized water in an 80 ml glass container. To this solution, 25.0 ml of 4 mM Na2S were added dropwise with vigorous stirring. The solution was exposed to 4 germicidal UV lamps G25T8 (the approximate UV energy is 12 μ ?? / mm2) for 1 hour under vigorous agitation. CdS / PDDA was formed by the addition of 0.50 ml of 2.68 mM Cd (N03) 2 to 0.50 ml of S2"/ irradiated PDDA.The resonance and UV-visible emission spectra are shown in Figure 22.

Example 29: Collapse of the polyanion with the Cd2 + / Pb2 + cations In a 400 ml plastic container of PAA (Sigma, average Mv 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were performed using narrow-range pH paper. 25 ml of a CdxPbi-x (N03) 2 solution was prepared by the addition of 5 mM Cd (N03) 2 and 5 mM Pb (N03) 2, as saline solutions in various proportions, where x = 0.1, 0.2, 0.3 , 0.4, 0.5, 0.6,. . . , 1. The total concentration of the metal ions in the final solution was 5 mM. 20 ml of PAA adjusted to pH and 25 ml of deionized water were obtained and placed in a 100 ml container. 15 ml of the metal solution were then added drop by drop under vigorous stirring to yield 60 ml of a Cdx2 + Pb2 + ix / IPAA solution with a final concentration of 1.25 mM final [Cdx2 + Pb2 + ix] solution and concentration end of PAA of 0.67 mg / ml.

Example 30: Collapse of the polyanion with the Cd2 + - g2 + cations In a 400 ml plastic container of PAA (Sigma, average Mv 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90sC) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. pH measurements were made using narrow interval pH paper. 25 ml of a solution of Cd0.gMg0.i (N03) 2 was prepared by mixing between 22.5 ml and 2.5 ml of solutions of 5 mM Cd (N03) 2 and 5 mM Mg (N03) 2, respectively. The total concentration of the metal ions in the final solution was 5 mM. 20 ml of PAA adjusted to pH and 25 ml of deionized water were obtained and placed in a 100 ml container. 15 ml of the metal solution were then added dropwise under vigorous stirring to produce 60 ml of a Cd2 + 0 solution. gMg2 + 0.9 / IPAA with a concentration of a final solution of [Cd2 + o.9Mg2 + 0.i] of 1.25 mM and final concentration of PAA of 0.67 mg / ml.

Example 31: Collapse of the polyanion with the Cd2 + -Zn2 + cations (90%) In a 400 ml plastic container of PAA (Sigma, average Mv 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90sC) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were performed using narrow-range pH paper. 10 ml of a solution of Cd0.iZn0.9 (N03) 2 was prepared by mixing together 1 ml and 9 ml of solutions of 5 mM Cd (N03) 2 and 5 mM Zn (N03) 2, respectively. The total concentration of the metal ions in the solution was 5 mM. 10 ml of PAA adjusted in pH were obtained and placed in a 50 ml container, followed by the dropwise addition of 10 ml of the metal salt solution under vigorous stirring to produce 20 ml of a Cd +0 solution. .iZn0.92 + / PAA with a final concentration of [Cd2 + 0.iZn2 + 0.9] of 2.5 mM and a final concentration of PAA of 1 mg / ml.

Example 32: Polyanion collapse with the Cd2 + -Zn2 + cations (10%) In a 400 ml plastic container of PAA (Sigma, average Mv 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 aC) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were performed using narrow-range pH paper. 6 ml of a solution of Cd0.9Zn0.i (N03) 2 was prepared by jointly mixing 5.4 ml and 0.6 ml of solutions of 5 mM Cd (N03) 2 and 5 mM Zn (N03) 2, respectively. The total concentration of the metal ions in the solution was 5 mM. 10 ml of PAA and 4 ml of deionized water adjusted for pH were obtained and placed in a 50 ml container, followed by the dropwise addition of 6 ml of the solution of the metal salt under vigorous stirring to produce 20 ml of a solution of Cd2 + o.9Zn2 + 0.i / PAA with a final concentration of [Cd2 + o.9Zn2 + 0.i] of 1.5 mM and a final PAA concentration of 1 mg / ml.

Example 33: Polyanion collapse with the Cd2 + / Mn2 + cations (1¾) In a 400 ml plastic container of PAA (Sigma, average Mv 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 aC) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. PH measurements were performed using narrow-range pH paper. 25 ml of a solution of Cdo.99Mno.01 (N03) 2 was prepared by co-mixing 24.75 ml and 0.25 ml of solutions of 5 mM Cd (N03) 2 and 5 mM Mn (N03) 2, respectively. The total concentration of the metal ions in solution was 5 mM. 20 ml of the adjusted PAA in pH and 25 ml of deionized water were obtained and placed in a 100 ml container. 15 ml of the metal solution were then added dropwise under vigorous stirring to produce 60 ml of a solution of Cd2 + 0.99Mn2 + o.oi / PAA with a final concentration of [Cd2 + or.99Mn2 + 0.oi] of 1.25 mM and a final PAA concentration of 0.67 mg / ml.

Example 34: Polyanion collapse with the Cd2 + / Hg2 + cations (50%) In a 400 ml plastic container of PAA (Sigma, average Mv 1.2 million) were dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M sodium hydroxide. pH measurements were made using narrow interval pH paper. 25 ml of a solution of Cdo.sHgo.s (NO3) 2 was prepared by jointly mixing 12.5 ml and 12.5 ml of the solutions of 5 mM Cd (N03) 2 and 5 mM Hg (N03) 2, respectively. The total concentration of the metal ions in solution was 5 mM. 20 ml of PAA adjusted to pH and 25 ml of deionized water were obtained and placed in a 100 ml container. 15 ml of the metallic solution were then added dropwise under vigorous stirring to yield 60 ml of a solution of Cd2 + o.5Hg2 + 0.5 / PAA with a final concentration of [Cd2 + o.5Hg2 + o.5l of 1.25 mM and a final PAA concentration of 0.67 mg / ml.

Example 35: Crosslinking of polyacrylic acid with 4 germicidal lamps G25T8 60 ml of Cdx2 + Pb2 + i-x / PAA were prepared according to Example 29 and placed in a 150.0 ml glass container. The solution was exposed to 4 germicidal UV lamps G25T8 (the approximate energy is 12 pW / mm2) for approximately 30 minutes under vigorous agitation. The irradiated solution was then dialysed against deionized water for 3 hours, changing the deionized water reservoir every hour. The PAA collapsed with CdxZni-x (N03) 2, CdxMni-x (N03) 2, CdxMgi_x (N03) 2 · · · was irradiated with UV in a similar manner for about 1 hour. The viscosity of the dialysed, irradiated, collapsed solutions was much lower than that of the non-irradiated, collapsed solutions. These solutions were filterable using a 0.2 μm nylon syringe filter.

Example 36: Cd0.5Pb0.5Te / PAA nanoparticles Under ambient conditions, 20 ml of Cdx2Pb2 + i-X / PAA produced according to Example 29 were placed in a 100 ml round bottom flask. The pH was adjusted to 11 using 1.1 M sodium hydroxide. PH measurements were made using narrow interval pH paper. To this solution, 20.4 mg of NaBH4 and 28.3 mg of trisodium citrate were added while the solution was being stirred. Immediately after the addition of borohydride and citrate, 0.625 ml of 0.02 M Na2 e03 were added. The solution develops a yellow color after the addition of the salt containing tellurium. The solution was then heated to reflux for approximately one hour under nitrogen atmosphere, to allow nanoparticles of CdPbTe / PAA to be formed. The absorbance and emission spectra of the resulting solution after one hour of reflux are shown in Figure 23. Unfortunately, the colloidal solutions were extremely unstable after exposure to air, and this was marked by a rapid disappearance of the spectra of characteristic absorbance and emission shown in Figure 23.

Example 37: Cdo.9Zno.1Te / PAA nanoparticles Under ambient conditions, 8 ml of Cd2 + o.9Zn2 + 0.i / PAA produced according to Example 32 were placed in a 25 ml round bottom flask, and reticle using the lamp allowed as described above. To this solution were added 15 mg of NaBH 4 and 30 mg of trisodium citrate while the solution was being fixed. Immediately after the addition of borohydride and citrate, 0.3 ml of Na2TeC > 3 0.01 M. The solution develops a peach color after the addition of the salt containing tellurium. The solution was heated to reflux then for approximately 2 hours to allow nanoparticles of CdZnTe / PAA to be formed. The absorbance and emission spectra of the resulting solution after two hours of reflux are shown in Figure 24.

Example 38: Nanoparticles of Cdo.99Mno.01Te / PAA Under ambient conditions, 10 ml of Cd2 + o.99 n2 + 0.oi / PAA produced according to Example 33 were placed in a 25 ml round bottom flask, and cross-linked using the allowed lamp as described above. To this solution were added 20 mg of NaBH4 and 37 mg of trisodium citrate while the solution was being fixed. Immediately after the addition of borohydride and citrate, 0.313 ml of Na2Te03 0.01 M were added. The solution develops a peach color after the addition of the salt containing tellurium. The solution was heated to reflux for approximately 2 hours to allow CdMnTe / PAA nanoparticles to be formed. The absorbance and emission spectra of the resulting solution after two hours of reflux are shown in Figure 25.

Example 39: Ndoparticles of Cdo.5Hgo.5Te / PAA Under ambient conditions, 10 ml of Cd2 + 0.5Hg2 + o.5 / PAA produced according to Example 34 were placed in a 25 ml round bottom flask, and cross-linked using the lamp allowed as described above. To this solution were added 16 mg of NaBH 4 and 29 mg of trisodium citrate while the solution was being fixed. Immediately after the addition of borohydride and citrate, 0.313 ml of Na2Te03 0.01 M were added. The remaining solution colorless after the addition of the salt containing tellurium. The solution was then heated to reflux for approximately 2 hours to allow nanoparticles of CdHgTe / PAA to be formed. However, the solution heated to reflux was not fluorescent.

Example 40: Formation of methylene blue / PAA nanoparticles In a 400 ml plastic container, 400.0 mg of PAA (Sigma, average Mv 1.2 million) was dissolved in 200 ml of deionized water. The plastic container was immersed in a hot water bath (approximately 80-90 ° C) and stirred vigorously for at least 30 minutes or until all the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 with 0.1 M sodium hydroxide. PH measurements were performed using narrow-range pH paper. 20.0 ml of this PAA solution were placed in a glass container and 20.0 ml of 5.0 mM aqueous methylene blue solution was added dropwise thereto under vigorous stirring. After all the methylene blue solution had been added, it was observed that the viscosity of the mixture was much lower than the original PAA solution. The resulting solution was exposed to UV radiation using 4 G25T8 germicidal UV lamps for 1.5 hours. The viscosity of the methylene blue / PAA solution irradiated with UV was lower than the viscosity of the solution not exposed to UV radiation. All literature and similar material cited in this application, including patents, patent applications, articles, books, treatises, dissertations and web pages, notwithstanding the format of such literature and similar materials, are expressly shared by reference in their whole. In the case where one or more of the literature and similar materials incorporated differs from or contradicts this application, including the defined terms, the use of terms, the techniques described or the like, this application controls. The section headers used here are for organizational purposes only and should not be considered as limiting the subject of interest described, in any way. While the present invention has been described in conjunction with various embodiments and examples, it is not intended that the present invention be limited to such embodiments or examples. On the contrary, the present invention encompasses various alternatives, modifications and equivalents, as will be appreciated by those of skill in the art. Consequently, descriptions, methods and diagrams should not be considered as limiting to the described order of elements, unless it is established for that purpose. Although this description has described and illustrated certain preferred embodiments of the invention, it should be understood that the invention is not restricted to those particular embodiments. Rather, the invention includes all modalities that are functionally or mechanically equivalent to the specific embodiments and features that have been described and illustrated. The claims should not be considered limited to the order described or elements described unless it is established for that purpose. It should be understood that various changes in form and detail may be made without departing from the scope of the appended claims. Therefore, all modalities that fall within the scope and spirit of the following claims and equivalents to it are claimed.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (69)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A method for producing a composite nanoparticle, characterized in that it comprises the steps of: a) providing a polymer solution that includes a polymeric material and a solvent; b) collapsing at least a portion of polymeric material around one or more precursor portions to form a composite precursor portion having an average diameter in the range of about 1 nm to about 100 nm; c) crosslinking the polymeric material of the composite precursor portion; and d) modifying at least a portion of the precursor portions of the composite precursor portion to form one or more nanoparticles, and thereby forming a composite nanoparticle.
2. 2. The method of compliance with the claim 1, characterized in that the composite nanoparticle has a mean diameter in the range of between about 1 nm and about 100 nm.
3. 3. The method according to claim 1, characterized in that the collapse step comprises the addition of a collapse agent to the polymer solution.
4. 4. The method according to claim 1, characterized in that the precursor portion is a collapsing agent.
5. 5. The method of compliance with the claim 4, characterized in that the collapsing agent comprises at least one ionic species.
6. 6. The method of compliance with the claim 5, characterized in that at least one ionic species is a salt and comprises one or more inorganic salts, organic salts or combinations thereof.
7. The method according to claim 1, characterized in that the modification step comprises exposing the composite precursor portion to electromagnetic radiation, to effect the formation of the nanoparticle from the precursor portion.
8. The method according to claim 1, characterized in that the modification step comprises subjecting the compound precursor portion to a chemical treatment.
9. The method according to claim 8, characterized in that the chemical treatment results in the reduction or oxidation of the precursor portion.
10. The method according to claim 8, characterized in that the chemical treatment comprises the addition of an opposite ion to a precursor portion of a compound precursor portion, or the opposite ion precursor, to effect the formation of the nanoparticle from the precursor portion.
11. 11. The method according to claim 1, characterized in that the solvent is an aqueous solution.
12. The method according to claim 1, characterized in that one or more precursor portions are one or more of a metal cation, complexed metal cation or complexed metal anion.
13. The method according to claim 12, characterized in that at least a portion of the precursor portions comprises two or more different metals; and wherein the nanoparticle formed by the modification step comprises an alloy of two or more of the two or more metals.
14. The method according to claim 1, characterized in that the polymeric material comprises linear or branched segments comprising polyions, the polyions comprising one or more anions, cations or combinations thereof.
15. 15. The method according to claim 1, characterized in that the polymeric material comprises one or more functional groups.
16. The method according to claim 1, characterized in that the polymeric material is covalently linked to the molecules capable of binding to the complementary binding partners, to form affinity binding pairs.
17. 17. The method according to claim 16, characterized in that the affinity binding pair is selected from the group consisting of protein-protein, protein-DNA, enzyme-substrate, antigen-antibody, DNA-DNA, DNA-AR, biotin-avidin, hapten-antihapten and combinations thereof.
18. The method according to claim 16, characterized in that the molecules covalently bound to the polymeric material are selected from the group consisting of protein, DNA ligand, oligonucleotide, aptamer, its nanoparticles and combinations thereof.
19. 19. The method according to claim 1, characterized in that the crosslinking step internally retreads the polymeric material of the composite precursor portion.
20. 20. A method for producing a nanoparticle material, characterized in that it comprises the steps of: a) providing a polymer solution comprising a polymeric material and a solvent; b) collapsing at least a portion of polymeric material around one or more precursor portions to form a composite precursor portion; c) crosslinking the polymeric material of the composite precursor portion; and d) modifying at least a portion of the precursor portions of the composite precursor portion to form one or more nanoparticles having an average diameter in the range of about 1 nm to about 100 nm, and thereby forming a composite nanoparticle; and e) subjecting the composite nanoparticle to pyrolysis to form a nanoparticle material.
21. 21. The method according to claim 20, characterized in that the pyrolysis substantially eliminates the polymeric material of the composite nanoparticle.
22. 22. The method according to claim 20, characterized in that the pyrolysis conditions are controlled such that the nanoparticle material formed comprises at least one nanoparticle partially coated with carbon.
23. 23. A composite nanoparticle, characterized in that it is made by a method according to claim 2.
24. 24. A nanoparticle at least partially coated with carbon, characterized in that it is made by a method according to claim 22.
25. 25. A composite nanoparticle , characterized in that it has a mean diameter in the range of between about 1 nm and about 100 nm, the composite nanoparticle comprises a nanoparticle substantially confined within an internally crosslinked polymeric material, wherein the nanoparticle comprises a metal alloy.
26. 26. The composite nanoparticle according to claim 25, characterized in that the metallic alloy comprises two or more of cadmium, zinc, copper, lead, silver, manganese, nickel, gold, magnesium, iron, mercury and platinum.
27. 27. A composite nanoparticle, characterized in that it has a mean diameter in the range between about 1 nm and about 100 nm, the composite nanoparticle comprises a nanoparticle substantially confined within an internally crosslinked polymeric material, wherein the nanoparticle comprises a metal alloy a compound that contains a metallic species.
28. 28. The composite nanoparticle according to claim 27, characterized in that the compound containing the metal species comprises one or more of a sulfide, selenide, telluride, chloride, bromide, iodide, oxide, hydroxide, phosphate, carbonate, sulfate, chromate and a combination of them.
29. 29. The composite nanoparticle according to claim 27, characterized in that it is capable of emitting electromagnetic radiation after absorption of energy.
30. 30. A composite nanoparticle, characterized in that it has a mean diameter in the range between about 1 nm and about 100 nm, the composite nanoparticle comprises a nanoparticle substantially confined within an internally crosslinked polymeric material, wherein the nanoparticle comprises a metal alloy a metallic element.
31. 31. The composite nanoparticle according to claim 30, characterized in that the elemental metal comprises cadmium, zinc, copper, lead, silver, manganese, nickel, gold, magnesium, iron, mercury or platinum.
32. 32. A method for producing a substrate coated with a material comprising nanoparticles, characterized in that it comprises the steps of: a) i) providing a first solution comprising a first polymeric material and a first solvent; ii) collapsing at least a portion of the first polymeric material around one or more first precursor portions to form a first composite precursor portion having an average diameter in the range of about 1 nm to about 100 nm; iii) crosslinking the first polymeric material of the first composite precursor portion; iv) modifying at least a portion of the first precursor portions of the first composite precursor portion, to form one or more first nanoparticles, and thereby form a first composite nanoparticle material, in the first solution; b) i) providing a second solution comprising a second polymeric material and a second solvent; ii) collapsing at least a portion of the second polymeric material around one or more second precursor portions to form a second composite precursor portion having an average diameter in the range of about 1 nm to about 100 nm; iii) crosslinking the second polymeric material of the second composite precursor portion; iv) modifying at least a portion of the second precursor portions of the second composite precursor portion, to form one or more second nanoparticles, and thereby forming a second composite nanoparticle material, in the second solution; c) contacting a substrate with at least a portion of the first composite nanoparticulate material, to form a first layer on at least a portion of the substrate; d) contacting at least a portion of the first layer with the solution containing a first charged compound, to form a second layer, the charged compound has a charge substantially opposite to that of the first composite nanoparticulate material; and e) contacting a substrate with at least a portion of the second composite nanoparticulate material, to form a third layer on at least a portion of the second layer.
33. 33. The method according to claim 32, characterized in that the first solution and the second solution are the same solution.
34. 34. The method according to claim 32, characterized in that the substrate is a thin film.
35. 35. The method according to claim 32, characterized in that at least one of the composite nanoparticulate materials comprises CdS / PAA and at least one of the charged compounds is poly (allylamine).
36. 36. The method of compliance with the claim 32, characterized in that one or more of the layers of the substrate form an optically active material.
37. 37. A method for producing a particle composed of a confined nanoparticle within a collapsed, crosslinked polymeric material, characterized in that it comprises: a) providing the polymeric material in a suitable solvent at a suitable concentration; b) providing an identity or a precursor thereof of the nanoparticle in the solvent; c) treating the polymeric material in the solvent with at least one collapsing agent to collapse the polymeric material; d) crosslinking the collapsed polymeric material; and e) treating the entity or the precursor thereof with a suitable production medium to produce the composite nanoparticle.
38. 38. The method according to claim 37, characterized in that the entity or a precursor thereof of the nanoparticle is at least one collapse agent.
39. 39. The method according to claim 37 or claim 38, characterized in that at least one collapse agent comprises at least one ionic species.
40. 40. The method according to claim 39, characterized in that at least one ionic species is the entity or a precursor thereof of the nanoparticle.
41. 41. The method according to claim 39 or claim 40, characterized in that the collapsing agent comprises ionic species that are provided by a salt selected from the group consisting of inorganic salts, organic salts, and a combination of inorganic and organic salts .
42. 42. The method according to any of claims 37 to 41, characterized in that the production means comprises a radiation passage.
43. 43. The method according to any of claims 37 to 41, characterized in the production means because it comprises suitable chemical treatment.
44. 44. The method according to claim 43, characterized in that the chemical treatment comprises a reduction or oxidation step.
45. 45. The method according to claim 43, characterized in that the chemical treatment comprises the addition of a suitable counter ion or a precursor of the opposite ion to effect the formation of the nanoparticle.
46. 46. The method according to any of claims 37 to 45, characterized in that the solvent is an aqueous solution.
47. 47. The method according to claim 37 or claim 38, characterized in that the entity or the precursor is a metal cation, complexed metal cation or complexed metal anion, and the production medium comprises the treatment of the cation or the anion complexed with radiation or an agent selected from a reducing agent or an oxidizing agent, to effect the production of the nanoparticle comprising the elemental metal.
48. 48. The method according to claim 47, characterized in that the precursor entity comprises ions selected from a metal cation or anions complexed from a plurality of metals, and the production medium comprises the treatment of cations or complexed anions, with radiation or an agent selected from a reducing agent or an oxidizing agent, to effect the production of the nanoparticle comprising an alloy of the elemental metals.
49. 49. The method according to any of claims 37 to 48, characterized in that the polymeric material comprises linear or branched segments including polyions selected from anions, cations or combinations thereof.
50. 50. The method according to any of claims 37 to 49, characterized in that the polymeric material comprises one or more functional groups.
51. 51. The method according to any of claims 37 to 50, characterized in that the polymeric material is conjugated to molecules capable of binding to the complementary binding partners, to form affinity binding pairs.
52. 52. The method according to claim 51, characterized in that the affinity binding pair is selected from the group consisting of protein-protein, protein-DNA, enzyme-substrate, antigen-antibody, DNA-DNA, DNA-AR, biotin-avidin, hapten-antihapten and combinations thereof.
53. 53. The method according to claim 51, characterized in that the molecules are selected from the group consisting of protein, DNA ligand, oligonucleotide, aptamer, its nanoparticles and combinations thereof.
54. 54. A method for the production of a nanoparticle, characterized in that it comprises the pyrolysis of the composite nanoparticle prepared by a method according to any of claims 37 to 53, wherein the nanoparticle is an elemental metal, alloy thereof, or a compound containing a metal species, to a effective temperature to effectively remove the polymeric material.
55. 55. A method for producing a nanoparticle totally or partially coated with carbon, characterized in that it comprises incompletely pyrolyzing the composite nanoparticle prepared by a method according to any of claims 37 to 53, wherein the nanoparticle is selected from the group which consists of an elemental metal, alloy thereof and a compound containing a metallic species, at an effective temperature to effect the production of the nanoparticle totally or partially coated with carbon.
56. 56. A composite nanoparticle, characterized in that it is made by a compound according to any of claims 37 to 53.
57. 57. The nanoparticle, characterized in that it is made by a method according to claim 54.
58. 58. A nanoparticle totally or partially carbon coated, characterized in that it is made by a method according to claim 55.
59. 59. A composite nanoparticle, characterized in that it comprises a nanoparticle confined within a polymeric, collapsed, crosslinked material, wherein the nanoparticle is selected from the group consisting of of an elemental metal, an alloy comprising the metal with at least one other metal, and a compound containing a metal species.
60. 60. The composite nanoparticle according to claim 59, characterized in that it is selected from the group consisting of an alloy comprising the metal with at least one other metal and a compound containing the metal species.
61. 61. The composite nanoparticle according to claim 60, characterized in that the compound containing the metal species comprises a compound selected from the group consisting of a sulfide, selenide, telluride, chloride, bromide, iodide, oxide, hydroxide, phosphate, carbonate , sulfate, chromate and a combination thereof.
62. 62. The composite nanoparticle according to any of claims 59 to 61, characterized in that the metal is selected from cadmium, zinc, copper, lead, silver, manganese, nickel, gold, magnesium, iron, mercury, platinum, and a combination thereof.
63. 63. The composite nanoparticle according to any of claims 56 to 62, characterized in that it is capable of emitting light after absorption of light energy.
64. 64. A coated substrate, characterized in that it has a plurality of layers of composite nanoparticles according to claim 56, sandwiched between adjacent layers of oppositely charged compounds.
65. 65. The coated substrate according to claim 64, characterized in that it is a film.
66. 66. The coated substrate according to claim 64 or 65, characterized in that the composite nanoparticle is CdS / PAA and the oppositely charged compound is poly (allylamine).
67. 67. The use of a composite nanoparticle according to claim 56, in the production of a substrate coated with multiple layers.
68. 68. The use of a composite nanoparticle according to claim 56, or 59 to 62, as an optically active material.
69. 69. The use of a nanoparticle according to claim 64 or claim 65, as an optically active material.