AU2011244891B2 - 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, said method 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. WO 20071041862 PCT/CA2006/001686 Absorbance Emission 0.5- L 300 400 500 600 700 Wavelength (nm) Fig. 1 SUBSTITUTE SHEET (RULE 26)

Description

AUSTRALIA Regulation 3.2 Patents Act 1990 Complete Specification Standard Patent APPLICANT: Vive Nano, Inc. Invention Title: COMPOSITE NANOPARTICLES, NANOPARTICLES AND METHODS FOR PRODUCING SAME The following statement is a full description of this invention, including the best method of performing it known to me: WO 20071041862 PCT/CA2006/001686 COMPOSITE NANOPARTICLES, NANOPARTICLES AND METHODS FOR PRODUCING SAME 5 FIELD OF THE INVENTION This invention relates to methods for producing composite nanoparticles comprising nanoparticles confined within cross-linked collapsed polymers, and 10 nanoparticles pr se; said composite nanoparticles, nanoparticles and carbon-coated nanoparticles. BACKGROUND OF THE INVENTION Nanoparticles are nanometer-sized materials e.g., metals, semiconductors, 15 polymers, and the like, possessing unique characteristics because of their small size. Nanoparticles in both 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 20 concentration of other species that may be present. The polymer can undergo conformational changes depending on the pH, ionic strength, cross-linking agents, temperature and concentration. For polyelectrolytes, at high charge density, e.g., when "monomer" units of the polymer are fully charged, an extended conformation is adopted due to electrostatic repulsion between similarly charged monomer units. 25 Decreasing the charge density of the polymer, either through addition of salts or a change of pH, can result in a transition of extended polymer chains to a more tightly packed globular i.e. collapsed conformation. The collapse transition is driven by attractive interactions between the polymer segments that override the electrostatic repulsion forces at sufficiently small charge densities. A similar transition can be 30 induced by changing the solvent environment of the polymer. This collapsed polymer is itself of nanoscale dimensions and is, itself, a nanoparticle. In this specification and claims the term "collapsed polymer" refers to an approximately globular form, generally as a spheroid, but also as an elongate or multi-lobed WO 2007/041862 PCT/CA2006/001686 conformation collapsed polymer having nanometer dimensions. This collapsed conformation can be rendered irreversible by the formation of intramolecular chemical bonds between segments of the collapsed polymer, i.e. by cross-linking. Macromolecules, i.e. polymers with the appropriate functional groups can 5 undergo inter-or intra-molecular cross-linking reactions to produce new materials or new molecules with distinct properties, such as for example, shape, solubility, thermal stability, and density. These reactions are important in making new materials and various schemes for chemical reactions leading to cross-linking are described in the literature. For example, US Patent 5,783,626 - Taylor et al, issued July 21, 1998, 10 describes a chemical method to cross-link allyl-functional polymers in the form of latexes, containing enamine moieties and pendant methacrylate groups via a free radical cross-linking reaction during film formation producing coatings with superior solvent resistance and increased thermal stability. Polymer cross-linking has also been used to stabilize semiconductor and metal nanoparticles. United States Patent 15 6,872,450 - Liu et a, issued March 29, 2005, teaches a method for stabilizing surface coated semiconductor nanoparticles by self assembling diblock polymers on the surface coating and cross-linking the functional groups on the diblock polymer. Similarly, United States Patent 6,649,138 - Adams et a], issued November 18, 2003, describes how branched amphipathic dispersants coated onto hydrophobic 20 nanoparticles can also be cross-linked to form a permanent cohesive over coating around the nanoparticle. Chemical means of cross-linking can be through radical reactions of pendant groups containing unsaturated bonds as described in aforesaid United States Patent 5,783,626. Another method is through the use of molecules having multifunctional 25 groups than can react with the functional groups of the polymer as described in aforesaid United States US Patent 6,649,138 and US Patent 6,872,450. Alternatively, cross-linking can be achieved though high energy radiation, such as gamma radiation. The most common method of preparing chalcogenide semiconductor nanocrystals is the TOP/TOPO synthesis (C.B. Murray, D.J. Norris, and M.G. 30 Bawendi, "Synthesis and Characterization of Nearly Monodisperse CdE (E = S, Se, Te) Semiconductor Nanocrystallites," J Am. Chem. Soe., 115:8706-8715, 1993). However, this method again involves multiple chemical steps and large volumes of 2 WO 2007/041862 PCT/CA2006/001686 expensive and toxic organometallic metal precursors and organic solvents. Furthermore, such nanoparticles need to be chemically modified in order to render them soluble in aqueous solution, which is important for a number of applications. Chalcogenide nanoparticles have also been synthesized in aqueous solution at low 5 temperature using water-soluble thiols as stabilizing agents ((a) Rajh, O.L. Midid, and A.J. Nozik, "Synthesis and Characterization of Surface-Modified Colloidal CdTe Quantum Dots," J Phys. Chem, 97: 11999-12003, 1993. (b) A.L. Rogach, L. Ktsikas, A. Komowski, D. Su. A. Eychmller, and H. Weller, "Synthesis and Characterization of Thiol-Stabilized CdTe Nanocrystals," Ber, Bunsenges. Phys. Chem., 100(11); 10 1772-1778, 1996. (c) A. Rogach, S. Kershaw, M. Burt. M. Harrison, A. Kornowski, A. Eychmulller, and H. Weller, "Colloidally Prepared HgTe Nanocrystals with Strong Room-Temperature Infrared Luminescence," Adv. Mater. 11:552-555, 1999. (d) Gaponik, N., D.V. Talapin, A.L. Rogach, K. Hoppe, E.V. Shevchencko, A. Kornowski, A. Eychmuller, H. Weller, "Thiol-capping of CdTe nanocrystals: an 15 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. Eychmflller, 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 20 with multiple processing steps and production of precursor gases. Another water based synthesis involves the formation of undesirable by-products that must first be removed before 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, 25 2003). CdTe nanocrystals are known to have tunable luminescence from green to red and have shown tremendous potential in light-emitting thin films (A.A. Mamedov, A. Belov, M. Giersig, N.N. Mamedova, and N.A. Kotov, "Nanorainbows: Graded Semiconductor Films from Quantum Dots," . Am. Chem. Soc., 123: 7738-7739, 30 2001), photonic crystals (A. Rogach, A. Susha, F. Caruso, G. Sukhoukov, A. Kornowski, S. Kershaw, H. Mbhwald, A. Eychmiller, and H. Weller, "Nano- and Microengincering: Three-Dimensinoal Colloidal Photonic Crystals Prepared from 3 WO 2007/041862 PCT/CA2006/001686 Submicrometer-Sized Polystyrene Latex Spheres Pre-Coated with Luminescent Polyelectrolyte/Nanocrystal Shells," Adv. Mater. 12:333-337, 2000), and biological applications (N.N. Memedova and N.A. Kotov, "Albumin-CdTe Nanoparticle Bioconjugates: Preparation, Structure, and Interunit Energy Transfer with Antenna 5 Effect," Nano Lett, 1(6):281-286, 2001). PbTe and HgTe materials exhibit tunable 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) A.L. Rogach, D.S. Koktysh, M. Harrison, and N.A. Kotov, "Layer-by-Layer Assembled Films of 10 HgTe Nanocrystals with Strong Infrared Emission," Chen, Mater., 12:1526-1528, 2000. (b) $. O'Conno, A. O'Riordan, H. Doyle, S. Moynihan, a. Cuddihy, and G. Redmond, "Near-Infrared Electroluminescent Devices Based on Colloidal HgTe Quantum Dot Arrays," Appl. Phys. Lett, 86: 201114-1 - 20114-3, 2005. (c) M.V. Kovalenko, E. Kaufmann, D. Pachinger, J. Roither, IM. Huber, J. Stang, G. Hesser, F. 15 Schaffler, 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. GOnes, H. Neugebauer, N.S. Sariicifci, J. Roither, M. Kovalenko, G. Pillwein, and W. Heiss, " Hybrid Solar Cells Using HgTe Nanocrystals and Nanoporous TiO 2 Electrodes," Adv. Funci. Mater. 20 16:1095-1099, 2006). PbTe, on the other hand, can be grown in a variety of glasses at high temperatures to produce composite materials for applications in optoelectronic devices ((a) A.F. Craievich, OL. Alves, and L.C. Barbosa, "Formation and Growth of Semiconductor PbTe Nanocrystals in a Borosilicate Glass Matrix," J. AppL Cryst., 30:623-627, 1997. (b) V.C.S. Reynoso, A.M. de Paula, R.F. Cuevas, JA. Medeiros 25 Neto, O.L. Alves, C.L. Cesar, and L.C. Barbosa, "PbTe Quantum Dot Doped Glasses with Absorption Edge in the 1.5 gm Wavelength Region," Electron. Lett., 31(12):1013-1015, 1995). Doping of CdTe with Hg results in the formation of CdHgTe composite nanocrystals. Red shifts in absorbance/phololuminescence spectra and enhanced PL 30 are observed with increasing Hg content (A.L. Rogach, M.T. Harrison, S.V. Kershaw, A. Kornowski, M.G. Burt, A. Eychmoller, and H. Weller, "Colloidally Prepared CdHgTe and HgTe Quantum Dots with Strong Near-Infrared Luminescence," phys. 4 WO 2007/041862 PCT/CA2006/001686 state. sol., 224(l):153-158, 2001). Cdi-HgxTe alloys are popular components in devices used for near-IR detector technology. A variety of methods have been developed to create these materials. US Patent 7,026,228 -- Hails et al, issued April 11, 2006, describes an approach to fabricating devices and semiconductor layers of 5 HgCdTe in a metal organic vapour phase epitaxy (MOVPE) process with mercury vapor and volatile organotelluride and organocadmium compounds. In a different approach, US Patents 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 the injection of organometallic precursor materials into organic solvents 10 (TOPTFOPO) at high temperatures, US Patent 6,126,740 - Schulz, issued October 3, 2000, discloses another non-aqueous method of preparing mixed-semiconductor nanoparticles from the reaction between a metal salt and chalcogenide salt in an organic solvent in the presence of a volatile capping agent. Mixtures of CdTe and PbTe have also been investigated for IR detection in the 15 spectral range of 3 to 5 pm. However, because these materials have such fundamentally different structures and properties (S. Movehan, 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. US Patent 5,448,098 20 Shinohara et al, issued September 5, 1995, describes a superconductive device based on photo-conductive ternary semiconductors such as PbCdTe or PbSnTe, Doping of telluride quantum dots, e.g. CdTe, with transition metals, e.g. Mn offers the possibility of combining optical and magnetic properties in one single nanoparticle ((a) S. Mackowski, T, Gurung, H.E. Jackson, LM. Smith, G. Karczewski, and J. Kossut, 25 "Exciton-Controlled Magnetization in Single Magnetic Quantum Dots," Appl. Phys. Lett. 87: 072502-1 - 072502-3, 2005. (b) T. KUmmel, C. Bacher, M.K. Welsch, D. Eisert, A. Forchel, B. Kunig, Ch. Becker, W. Ossau, and G. Landwehr, "Semimagnetic (Cd,Mn)Te Single Quantum Dots - Technological Access and Optical Spectroscopy," J Crys. Growth, 214/215:150-153, 2000). Unfortunately, these 30 materials are mostly fabricated using thin-film technologies such as molecular beam epitaxy or chemical vapour deposition and the necessity for a very controlled environment during growth makes these materials inaccessible. Some mixed-metal 5 WO 20071041862 PCT/CA2006/001686 tellurides such as CdHgTe (S.V. Kershaw, M. Burt, M. Harrison. A. Rogach, H. Weller, and A. Eychmlhler, "Colloidal CdTe/HgTe Quantum Dots with High Photo] uminesenece quantum Efficiency at Room Temperature," Appl. Phys. Lett., 75: 1694-1696, 1999); and CdMnTe (N.Y. Morgan, S. English, W. Chen, V. 5 Chernornordik, A. Russ, P.D. Smith, A. Gandjbakhche, "Real Time In Vivo Non Invasive Optical Imaging Using Near-Infrared Fluorescent Quantum Dots," Acad. Radio, 12(3): 313-323, 2005) quantum dots have been prepared in aqueous solution which is an adaptation of the synthetic technique outlined in supr Rajh, OL. et al. However, all of the aforementioned methods involve many processing steps, 10 sophisticated equipment or large volumes of expensive and toxic organometallic metal precursors and organic solvents. A simple tellurite reduction method to prepare cadium telluride materials has been used using sodium tellurite (NazTEO 3 ) as a tellurium precursor salt with a suitable reducing agent, such as NaBH 4 with M2' cations (H. Bao, E. Wang, and S. 15 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 an environmentally friendly, "one pot", cost-effective, and generalizable method of directly producing metallic, metallic alloyed, semiconductor, oxide, and other forms of nanocomposite particles having 20 effective functionality in a multitude of scientific disciplines. SUMMARY OF THE INVENTION In various aspects, the present invention provides methods of producing a 25 composite nanoparticle comprising a nanoparticle confined within a cross-linked collapsed polymeric material, which is itself a nanoparticle. The term "composite nanoparticle" in this specification, means a nanoparticle substantially confined within a cross-linked, polymeric material. In various aspects, the present invention provides said composite nanoparticles 30 when made by the methods of the present inventions. In various aspects, the present invention provides methods for providing non encapsulated nanoparticles from the aforesaid composite nanoparticles. 6 WO 2007/041862 PCT/CA2006/001686 In various aspects, the present invention provides methods for producing wholly or partially carbon-coated nanoparticles from said composite nanoparticles. In various embodiments, the present inventions teache the ability to make a wider variety of composite nanoparticles, including oxide, semiconductor, and more 5 complex composite nanoparticles. In various aspects, the present inventions provide methods for producing a composite nanoparticle comprising the steps of: a) providing a polymeric solution comprising a polymeric material and a solvent; 10 b) collapsing at least a portion of the polymeric material about one or more precursor moieties to form a composite precursor moiety having a mean diameter in the range between about I nm and about 100 nm; c) cross-linking the polymeric material of said composite precursor 15 moiety; and d) modifying at least a portion of said precursor moieties of said composite precursor moiety to form one or more nanoparticles and thereby forming a composite nanoparticle. "Confined" in this specification means that the nanoparticle is substantially 20 within the limits of the collapsed polymer's dimensions and includes, but is not limited to, the situation wherein portions of the polymer may be strongly interacting with the nanoparticle within the polymer dimensions. As used herein, the term "precursor moiety" refers to a compound or entity at least a portion of which is a component of the eventual nanoparticle formed and 25 includes nanoparticle precursors. A polymeric material of use in the practice of the present inventions can be any molecule capable of collapse that contains units of monomers, that can be synthetic or naturally occurring and can be linear, branched, hyperbranched, or dendrimeric. Non-limiting examples of suitable polymeric materials are discussed in 30 the various examples, which include, but are not limited to, poly(diallyldimcthylammonium chloride) (PDDA), and polyacrylic acid (PAA), poly(styrene sulfonic acid) (PSS), 7 WO 20071041862 PCT/CA20061001686 It also can be any polymer containing ionized or ionizable moieties along its length and is of sufficient length such that the collapsed form has nanometer dimensions. The collapsed form can be of different morphologies, such as, for example, spherical, elongated, or multi-lobed. The dimensions in any direction are 5 anywhere from 0.1 to 100 nm, and preferably 1-50 nm. A wide variety of solvents can be used to form a polymeric solution of use in the present inventions. In various embodiments, the polymeric solution is preferably an aqueous solution. In preferred embodiments of the present inventions, a chosen polymer is 10 dissolved in a suitable solvent to form a solution of the polymer. The solvent can 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 polymer which substantially surrounds, e.g., confines, a precursor moiety. The collapsing agent can itself be the precursor moiety. The chosen confined agent, for example a precursor 15 moiety, can be, e.g., an organic or inorganic charged ion or a combination thereof. For example, the confined agent can be an ion from an organic salt, an inorganic salt, or an inorganic salt that is water soluble where the water soluble inorganic salt is of the form MAy where M is a metal cation belonging to Groups I to IV of the Periodic Table possessing a charge +y and A is the counter ion to M with a charge -x or a 20 combination thereof. The confined agent could further comprise a mixture of ions from at least two inorganic salts. Collapsing agents are usually water-soluble inorganic salts, most preferably, those that contain metal cations and their corresponding anions, both of which are known to induce a collapse-transition for certain polymeric materials. Non-limiting 25 examples are Cd(NO 3 )2, Zn(N03) 2 , Cu(SO 4 ), Pb(N0 3

)

2 , Pb(CH 3

COO)

2 , Ag(N0 3 ), Mn(S0 4 ), Ni(NO3) 2 . A variety of techniques can be used to collapse the polymeric material around a precursor moiety. For example, in various embodiments a collapsing agent such as a different solvent, an ionic species (e.g., a salt); or combinations thereof can be used. 30 In various embodiments, it is preferred that the precursor moiety itself serve as a collapsing agent. Multiple collapsing agents can be used . 8 WO 2007/041862 PCT/CA2006/001686 In various embodiments the at least one collapsing agent preferably comprises at least one ionic species. Preferably, in various embodiments, the at least one ionic species is a precursor moiety. In various embodiments, the precursor moiety comprises at least one metal 5 cation, complexed metal cation, or complexed metal anion. In various embodiments where the precursor moiety comprises a metal cation, complexed metal cation, or complexed metal anion, the modifying step (production means) comprises treating the cation, complexed cation, or complexed anion with y-radiation or an agent selected from a reducing agent or an oxidizing agent to effect production of the nanoparticle 10 comprising elemental metal confined within the cross-linked, collapsed polymeric material. In various embodiments, the precursor moiety comprises two or more different metals. In various embodiments where the precursor moiety comprises two or more different metals, the modifying step comprises forming an alloy of two or more of the 15 two or more metals. In various embodiments, the precursor moiety comprises ions selected from a cation, complexed cations, or complexed metal anions of a plurality of metals and the modifying step comprises treating the cations or complexed anions with radiation, for example, y-radiation, or an agent selected from a reducing agent or an oxidizing agent 20 to effect production of the nanoparticle comprising an alloy of said metals, confined within the cross-linked collapsed polymeric material. In various embodiments, the precursor moiety comprises a metal species containing compound. By the term "metal species-containing compound" is meant a compound 25 containing 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 metal species-containing compound, the metal is preferably Cd, Zn, Cu, Pb, Ag, Mn, Ni, Au, Mg, Fe, Hg, Pt or a combination thereof. In various embodiments of the present inventions having a metal species 30 containing compound, said compound containing said metal species preferably comprises one or more of a sulphide, selenide, telluride, chloride, bromide, iodide, oxide, hydroxide, phosphate, carbonate, sulphate, chromate and a combination thereof 9 WO 2007/041862 PCT/CA2006/001686 In various embodiments, a composite precursor moiety formed by a method of the present inventions has a mean diameter in the range between about I nanometer (nm) to about 100 nm. In various embodiments, the composite precursor moiety has a mean diameter in one or more of the ranges between: (a) about 1 nm to about 1 Onm; 5 (b) about 10nm to about 30nm; (c) about 15 nm to about 50 nm; and (d) about 50nm to about 1 00nm). It is to be understood that the term "mean diameter" is not meant to imply any sort of specific symmetry (e.g., spherical, ellipsoidal, etc.) of a composite precursor moiety. Rather, the composite precursor moiety could be highly irregular and asymmetric. 10 The formation of intra-molecular covalent bonds that effects the cross-linking of the polymeric material can be induced either by chemical means or by irradiation. Chemical means of cross-linking can also be achieved through the use of multi dentate molecules as cross-linkers. These molecules contain multiple functional groups that are complementary to, and, therefore, can form covalent bonds with the 15 functional groups on the polyelectrolyte polymeric material. These molecules can be linear, branched, or dendrimeric. For example, a molecule containing multiple amine groups, such as 2,2'-ethylenedioxydiethylamine can effect the intramolecular cross linking of collapsed poly(acrylic acid). The cross-linking reaction in this case is promoted by the addition of an activating agent, typically used for amide bond 20 formation, such as a carbodiimide. The chemical cross-linking can be carried out to derivatize the polymer, such that a fraction of the ionizable groups are converted to groups that can be cross-linked through free-radical reactions. An example is to convert some of the carboxylic acid groups of poly(acrylic acid) to allyl esters. The allyl groups can then be reacted to 25 form intramolecular bonds through radical chemistry. Cross-linking by irradiation can be effected by exposing a solution of the collapsed polymer to an electromagnetic radiation source. The radiation source can be, for example, an excimer laser, a mercury arc lamp, a light emitting diode, UV germicidal lamp radiation or gamma rays, 30 A variety of techniques can be used in the present inventions to modify at least a portion of said precursor moieties of said composite precursor moiety to form one or more nanoparticles and thereby form a composite nanoparticle. These techniques are 10 WO 20071041862 PCT/CA2006/001686 also referred to as "production means" herein since they are used in the production of the nanopareticle. Suitable techniques for modifying a precursor moiety to form the desired nanopartilce include, but are not limited to, exposure to electromagnetic radiation, 5 chemical treatment, and combinations thereof. Examples of suitable electromagnetic radiation exposure, include, for example y-radiation, ultraviolet radiation, infrared radiation, etc. In various embodiments, the electromagnetic radiation is coherent radiation, such as provided, e.g., by a laser, in others it is incoherent, such as provided, e.g., by a lamp. Examples of chemical treatments include, but are not 10 limited to, contacting with an oxidizing agent, contacting with a reducing agent, addition of at least one counter ion, a compound containing the counter ion, or a precursor to the counter ion, where the counter ion is a counter ion with respect to the precursor moiety or a portion thereof. Generally, modification of the precursor moiety results in the formation of a nanoparticle that is no longer soluble within the 15 solvent of the polymeric solution. Reaction either by reduction or oxidation of the ions, ionic precursor moieties, within the cross-linked polymeric material to form the composite nanoparticles can be effected through chemical, electrocebemical, or photochemical means. The resultant nanoparticles can be, for example, semiconductor crystals, 20 including, but not limited, to CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, PbS, PbSe, PbTe, CuI, H1gS, 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 between about 1 nanometer (Onm) to about 100 nm. In various embodiments, the composite nanoparticle has a mean 25 diameter in one or more of the ranges between: (a) about Inm to about lOnm; (b) about (Onm to about 30nm; (c) about 15 nm to about 50 nm; and (d) about 50nm to about I 00nm). It is to be understood that the term "mean diameter" is not meant to imply any sort of specific symmetry (e.g., spherical, ellipsoidal, etc.) of a composite nanoparticle. Rather, the composite nanoparticle could be highly irregular and 30 asymmetric. In various embodiments, the nanoparticle, formed from a precursor moiety, comprises an alloy of two or more different metals. In various embodiments where I I WO 2007/041862 PCT/CA2006/001686 the precursor moiety comprises two or more different metals, the modifying step comprises forming an alloy of two or more of the two or more metals. in various embodiments, the nanoparticle, formed from a precursor moiety, comprises a metal species-containing compound. By the term "metal species 5 containing compound" is meant a compound containing 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 metal species-containing compound, the metal is preferably Cd, Zn, Cu, Pb, Ag, Mn, Ni, Au, Mg, Fe, Hg, Pt or a combination thereof. 10 In various embodiments of the present inventions having a metal species containing compound, said compound containing said metal species preferably comprises one or more of a sulphide, selenide, telluride, chloride, bromide, iodide, oxide, hydroxide, phosphate, carbonate, sulphate, chromate and a combination thereof. 15 In various aspects., the present inventions provide methods for producing a nanoparticle material, comprising the steps of: (a) providing a polymeric solution comprising a polymeric material and a solvent; (b) collapsing at least a portion of the polymeric material about one or more precursor moieties to form a composite precursor moiety; (c) cross-linking the polymeric material of said composite precursor 20 moiety; and (d) modifying at least a portion of said precursor moieties of said composite precursor moiety to form one or more nanoparticles having a mean diameter in the range between about 1 nm and about 100 nm and thereby forming a composite nanoparticle; and (e) pyrolysing said composite nanoparticle to form a nanoparticle material. In various embodiments, the pyrolysis conditions are 25 controlled such that the nanoparticle material formed comprises at least a partially carbon-coated nanoparticle In various embodiments, the present inventions provide methods for producing a metal nanoparticle, comprising pyrolysing the composite nanoparticle prepared by a method of the present inventions described herein, wherein the metal nanoparticle is 30 an elemental metal, an alloy comprising the metal with at least one other metal, or a metal species-containing compound, at a temperature to effective to substsantailly remove the polymeric material. 12 WO 2007/041862 PCT/CA2006/001686 In various embodiments, the present inventions provide methods for producing a carbon-coated metal nanoparticle comprising incompletely pyrolysing the composite nanoparticle prepared by a method of the present inventions described herein, wherein the metal nanoparticle is selected from an elemental metal, an alloy comprising the 5 metal with at least one other metal, and a metal species-containing compound, at a temperature to effect production of the carbon-coated metal nanoparticle. In various aspects, the present inventions provide composite nanoparticles when made by a method or process of one of the inventions described herein. In various aspects, the present inventions provide non-confined and wholly or 10 partially carbon-coated metal nanoparticles when made by methods of the present inventions described herein. Various embodiments of the present inventions can be of value in the production of semiconductor nanopartices, including, for example, quantum dots such as CdSe, CdS, CdTe, and others. Various embodiments of the present inventions 15 can be of value in the production of complex salts, such as LiFePO 4 , and oxide particles, such as Fe 2 0 3 Accordingly, in an various embodiments, the precursor moiety comprises at least one metal cation, complexed metal cation, or complexed metal anion, and the production means (modifying step) comprises treating the metal cation, complexed 20 cation, or complexed anion with a suitable counterion or precursor thereof to effect production of the composite nanoparticle comprising a metal species-containing compound. In various embodiments, the precursor moeity comprises an anion, and the modifying step (production means) comprises treating the anion with a suitable metal 25 counterion or precursor thereof to effect production of the composite nanoparticle comprising a metal species-containing compound. In various aspects, the modifying step comprises use of a suitable counterion or precursor thereof to effect production of a semiconductor nanoparticle or composite nanoparticle. 30 In a various aspects, the modifying step comprises use of a suitable counterion or precursor thereof to effect production of a composite nanoparticle comprising a complex salt. 13 WO 2007/041862 PCT/CA2006/001686 In a various aspects, modifying step comprises use of a suitable counterion or precursor thereof to effect production of a nanoparticle comprising a hydroxide. In a preferred aspect, the hydroxide may be subsequently heated to convert the hydroxide to an oxide. 5 The aforesaid composite nanoparticles comprising a metal species-containing compound, a complex salt, hydroxide, or oxide, a semiconductor entity, can be , in various embodiments, effectively pyrolysed to substantially remove the polymeric material, or to only partially remove the polymeric material to produce, for example, a wholly or partially carbon-coated nanoparticle. 10 Thus, various embodiments of the present inventions relate to methods of making composite nanoparticles and nanoparticles that may have a wide variety of applications in a variety of sectors, including, but not limited to, biology, analytical and combinatorial chemistry, catalysis, energy and diagnostics. By utilizing starting materials that are readily soluble in water, the present inventions, in various 15 embodiments, can provide nanoparticles and composite nanoparticles having unique characteristics applicable in the aforesaid sectors, which nanoparticles may be water soluble. The synthesis routes of various embodiments of the present inventions, include, but are not limited to, synthesis in a "one pot" system in an aqueous medium. 20 The particle size can be controlled, for example, by varying the molecular weight of the polymer, the degree of internal cross-linking, solution conditions and the amount of collapsing agent added. The polymer coat can be chosen to have desirable functional groups that can impart desirable properties, for example, having the capability for attachment to molecules, such as proteins or to enhance or decrease the 25 sticking to substrates. In various embodiments, the present inventions provide methods for making water-dispersable composite nanoparticles with inherent chemical functional groups that can be reacted with complementary functional groups on other molecules. Water dispersable, in this context, refers to the formation of composite nanoparticles that can 30 be prevented from aggregation in aqueous solution through adjustment of solution conditions. 14 WO 2007/041862 PCT/CA2006/001686 In various embodiments, the methods of the present inventions 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. 5 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 can 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 polymer which substantially surrounds, e.g., confines the agent therein. The chosen confined agent 10 can be an organic or inorganic charged ion or a combination thereof. For example, the confined agent can be an ion from an organic salt, an inorganic salt, or an inorganic salt that is water soluble where the water soluble inorganic salt is of the form MxAy where M is a metal cation belonging to Groups I to IV of the Periodic Table possessing a charge +y and A is the counter ion to M with a charge -x or a 15 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, cross-linking of the collapsed polymer is achieved by exposing the polymer to y radiation or UV radiation, Preferably, the UV radiation is UV laser radiation or UV 20 are lamp radiation. In various embodiments, the intra-molecular cross-links of the intra-molecular cross-linking process are chemically produced, for example, with carbodiimide chemistry with a homobifunctional cross-linker. One preferred embodiment of the present inventions involves the formation of composite nanoparticles by the addition of ions that induce precipitate formation of 25 the confined agent within the collapsed polymeric material, wherein the collapsed polymer is intra-molecularly cross-linked. As used herein, "precipitation" of a confined ion referes to modification of the ion to a compound that is substantially insoluble in the solvent of the polymeric solution. Various preferred embodiments of the aspects of the present inventions 30 include, but are not limited to, using polymers dissolved in a solvent, usually water, so as to make a dilute solution. Polymers with ionizable groups, for example, NH 2 , RNH, and COON can be chosen because of their water-solubility under appropriate 15 WO 2007/041862 PCT/CA20061001686 solution conditions and their ability to undergo a collapse transition when exposed to certain concentrations of ions in solution, usually through addition of an inorganic salt. The collapse of the polymer brings about the confinement of some of the ions within a collapsed polymeric structure. In order to make the collapsed conformation 5 of the polymers permanent, intra-macromolecular bond formation is facilitated either through radiation exposure, through the use of chemical cross-linkers, or both, in various embodiments, the collapsed intra-molecular, cross-linked polymer have 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 10 be reduced, oxidized, and/or reacted (eg. by precipitation with an external agent), which results in the formation of the composite nanoparticle of the inner nanoparticle confined within the collapsed intra-molecular cross-linked polymeric material. Un reacted ionizable groups, for example, can serve as future sites for further chemical modification, dictate the particles solubility in different media, or both. 15 An ionizable moiety or group is any chemical functional group that can be rendered charged by adjusting solution conditions, while ionized moieties refers to chemical functional groups that are charged regardless of solution conditions, The ionized or ionizable moiety or group can be either cationic or anionic, and can be continuous along an entire chain as in the case of regular polymers, or can be 20 interrupted by blocks containing different functional groups, as in the case of block polymers. In various embodiments, a preferred cationic group is the amino group and preferred anionic groups are carboxylic acid, sulfonic acid, phosphates, and the like. For cationic polymers, examples are poly(allylamine), poly(ethyleneimine) 25 poly(diallyldimethylarnmonium chloride, and poly(lysine). For anionic polymers, examples are poly(acrylic acid), poly(styrene sulfonic acid), poly(glutamic acid), etc. Block polymers are made up of blocks of polymers 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 30 property to the block polymer. In various embodiments, functional groups of the polymeric material can be used for conjugating the composite nanoparticles to other molecules containing 16 WO 2007/041862 PCT/CA20061001686 complementary functional groups. These molecules can be any member of affinity binding pairs such as antigen-antibody, DNA-protein, DNA-DNA, DNA-RNA, biotin-avidin, hapten-antihapten, protein-protein, enzyme-substrate and combinations thereof. These molecules can also be protein, ligand, oligonucleotide, aptamer, 5 carbohydrate, lipid, or other nanoparticles. An example is the conjugation of poly(acrylic acid)-encased nanoparticles to proteins through amid bond formation between amine groups on proteins and the carboxylic acid groups on poly acrylic acid (PAA). A fraction of the functional groups of the polyelectrolyte polymer can also be 10 modified to convert them to other functional groups that can be used for conjugation. For example, a hetero bi-functional molecule containing an amine group and a latent thiol group can be reacted with poly(acrylic acid)-encased nanoparticles through amide bond formation thereby converting the carboxylic acid to a thiol group. The thiol group can be used for conjugation to other molecules containing thiol-reactive 15 groups. The wide variety of potential applications for the 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, and IR light, wherein the composite nanoparticle or nanoparticle are used as 20 pigments or are incorporated into an optical device. In various embodiments, afer absorbing light energy the composite nanoparticle may be capable of emitting light. In various embodiments of the present inventions, provided are methods wherein the polymeric material is conjugated to molecules containing functional groups for binding to complementary binding partners to form an affinity-binding pair 25 selected from the group having an enzyme-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 inventions 30 may be used, e.g., to enhance spectroscopic techniques, including vibrational spectroscopy. 17 WO 20071041862 PCT/CA2006/001686 In various embodiments, provided are methods wherein the composite nanoparticles are further assembled on a surface of a substrate using layer-by-layer assembly or further aggregated into three-dimensional systems of composite nanoparticles, whereby the three-dimensional systems are created on a surface. In 5 various embodiments this substrate is a film Accordingly, in various aspects the present inventions provide a coated substrate having a plurality of layers of composite nanoparticles as hereina described interspersed between adjacent layers of oppositely charged compounds. In various embodiments, a coated substrate as herein described is preferably 10 coated, with a composite narioparticle of CdS/PAA and the oppositely charged compound is poly(allylamine) hydrochloride (PAH). In various embodiments, the present inventions provide use of a composite nanoparticle as herein described in the production of a multi-layered coated substrate. This substrate could be of value, for example, as one or more of: (a) a solid substrate 15 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. In various embodiments, the compounds according to the present inventions could be of value as semiconductor materials, for example, as quantum dots. 20 BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other aspects, embodiments, objects, features and advantages of the present inventions can be more fully understood from the following 25 description in conjunction with the accompanying drawings. In the drawings, like reference characters generally refer to like features and structural elements throughout the various figures. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the present inventions, wherein. Figure I represents UV-Vis absorption spectra of CdS/PAA composite 30 nanoparticles prepared according to Example )3; Figure 2 represents emission spectra of different CdS/PAA composite nanoparticles prepared according to Example 13; is WO 2007/041862 PCT/CA2006/001686 Figure 3 represents STEM image of CdS/PAA composite nanoparticles prepared according to Example 13; Figure 4 represents uv-vis absorption and emission spectra of CdSe/PAA composite nanoparticles prepared according to Example 14; 5 Figure 5 represents uv-vis absorption and emission spectra of (CdSe CdS)/PAA composite nanoparticles prepared according to Example 15; Figure 6 represents uv-vis absorption and emission spectra of CdTc/PAA composite nanoparticles prepared according to Example 16; Figure 7 represents uv-vis absorption and emission spectra of (CdTe 10 ZnS)/PAA composite nanoparticles produced according to Example 17; Figures 8(a)-8(c) represent STEM with EDX analysis of LiFePO 4 /PAA composite nanoparticles produced according Example 18; Figure 9 represents a XRD pattern of LiFePO 4 /PAA composite nanoparticles produced according Example 18; 15 Figures 10(a)-10(c) represents STEM with EDX analysis of Fe 2 0 3 /PAA composite nanaparticles produced according Example [9; Figure iI represents an XRD x-ray diffraction pattern of Fe 2

O

3 /PAA composite nanoparticles produced according to Example 19; Figure 12 represents STEM image of ZnO/PAA composite nanoparticles made 20 according to Example 20; Figure 13 represents uv-vis absorbance and emission spectra of ZnO/PAA composite nanoparticles made according to Example 20; Figure 14 represents emission spectra of both CdS/PAA composite nanoparticles coated and non-coated polystyrene prepared according to Example 21; 25 Figure 15 represents uv-vis absorption spectra of Ag/PAA composite nanoparticles produced according to Example 22; Figure 16 represents a STEM image of Ag/PAA composite nanoparticles produced according to Example 22; Figure 17 represents uv-vis absorption spectra of Au/PAA composite 30 nanoparticles produced according to Example 23; Figure 18 represents STEM image of Au/PAA composite nanoparticles produced according to Example 23; 19 WO 2007/041862 PCT/CA2006/001686 Figure 19 represents uv-vis spectra of (Au, Ag)/PAA composite nanoparticles produced according to Example 24; Figures 20(a)-20(c) represent STEM with EDX analysis image of (Au, Ag)/PAA composite nanoparticles produced according to Example 24; 5 Figure 21 represents uv-vis and emission spectra of CdS/PSS composite nanoparticles produced according to Example 27; Figure 22 represents uv-vis and emission spectra of CdS/PDDA composite nanoparticles produced according to Example 28; and Figure 23 represents absorbance and emission spectra of CdPbTe/PAA 10 composite nanoparticles produced according to Example 36 according to the present invention; Figure 24 absorbance and emission spectra of CdZnTe/PAA composite nanoparticles produced according to Example 37 according to the invention; and Figure 25 absorbance and emission spectra of CdMnTe/PAA composite 15 nanoparticles produced according to Example 38 according to the present invention. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS EXAMPLES In the following examples, the term 20 (a) "M" /polymer refers to the collapsed polymeric material with the metal cation My', wherein M is the stated metal in the example; and (b) A" / polymer refers to the collapsed polymeric material collapsed with the anion A'. In the case of multiple cations or anions used to collapse a single polymer, the 25 different metal cations and anions will be separated by a comma "," as in the case (M I, M9 2 , etc. .)/Polymer and (A," , A 2 4, etc... )/Polymer (eg Cd 2 t/PAA, Cf /PDDA, etc.). Nanoparticles formed from the metal ions will be designated as M, ,j Ai y1 /Polymer (eg. CdS/PAA, (CdS. PbS)/PAA, etc). Nanoparticles formed from the metal ions that have been treated with another agent to form a different material will 30 be designated by a "-" as in (Mi 1 A, yi - M2yA 2 y)/Polymer (eg. (CdSe-CdS)/PAA, (CdTe-ZnS)/PAA, etc). 20 WO 2007/041862 PCT/CA2006/001686 Example 1: Polycation collapse with (-1) anion In a plastic 400.0 ml beaker, 3.0 ml of poly(diallyldimethylammonium 5 chloride) (PDDA) [Sigma, Average M, 400-500K, 20 wt% in water] was diluted to 300 ml with deionized water. The solution was stirred for 10 minutes. 5.0 ml aliquots were obtained, and placed in 20 mi scintillation vials. To each was added dropwise with vigorous stirring 5.0 ml of aqueous NaCl solutions of different concentrations (2 mM - 60 mM) yielding 10 mL of CI/PDDA solutions with different 10 [CE] between I 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 NaCl concentration changed suddenly at approximately 10 mM; this was taken as the PDDA collapse point with C. such that at lower concentrations, the PDDA is primarily in an extended configuration. 15 Example 2: Polycation collapse with (-2) anion In a plastic 400.0 ml beaker, 3.0 ml of poly(diallyldimethylammonium chloride) (PDDA) [Sigma, Average M,400-500K, 20 wt% in water] was diluted to 20 300 ml with deionized water. The solution was stirred for 10 minutes. 5.0 ml aliquots were obtained, and placed in 20 ml scintillation vials. To each was added dropwise with vigorous stirring 5.0 ml of aqueous Na 2

SO

4 solutions of different concentrations (2 mM - 20 mM) yielding 10 mL of SOJ/PDDA solutions with different [SO ] between 1 and 10 mM and a final PDDA concentration of I mg/m1. 25 The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of NaCl concentration changed suddenly at approximately 3 mM; this was taken as the PDDA collapse point with SQ42 , such that at lower concentrations, the PDDA is primarily in an extended configuration. 30 Example 2: Polycation collapse with (-3) anion In a plastic 400.0 ml beaker, 15 ml of poly(diallyldimethylammonium chloride) (PDDA) [Sigma, Average Mw 400-500K, 20 wt% in water] was diluted to 300 ml with deionized water. The solution was stirred for 10 minutes. 5.0 ml 35 aliquots were obtained, and placed in 20 ml scintillation vials. To each was added 21 WO 20071041862 PCT/CA2006/001686 dropwise with vigorous stirring 5.0 ml of aqueous Na 3

PO

4 solutions of different concentrations (2 mM - 50 mM) yielding 10 mL of POY-/PDDA solutions with different [PO] between I and 25 mM and a final PDDA concentration of 5 mg/ml. The relative viscosity of each solution was measured with an Ostwald viscometer. 5 The viscosity as a function of NaCI concentration changed suddenly at approximately 2 mM; this was taken as the PDDA collapse point with P02- , such that at lower concentrations, the PDDA is primarily in an extended configuration. Example 4: Polyanion collapse with (+1) cation. 10 In a 400 ml plastic beaker, 400.0 mg of (PAA) (Sigma, Average Mv 1.2 million) was dissolved in 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 * C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled 15 to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. pH measurements were done using narrow range pH paper. 5 ml aliquots of the pH adjusted PAA were obtained and to each was added 5.0 ml aliquots were obtained, and placed in 20 ml scintillation vials. To each was added dropwise with vigorous stirring 5.0 ml of aqueous NaCl solutions of different concentrations (0.2 mM - 10,0 20 mM) yielding 10 mL of Nat/PDDA solutions with different [Na] between 0.1 mM and 5.0 mM and a final PAA concentration of I mg/ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of NaCI concentration changed suddenly at approximately 2 mM; this was taken as the PAA collapse point with Nat such that at lower concentrations, the PAA is primarily 25 in an extended configuration. Example 5: Polyanion collapse with (+2) cation. 30 In a 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average M. 1.2 million) was dissolved in 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 " C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. pH measurements 35 were done using narrow range pH paper. 5 ml aliquots of the pH adjusted PAA were 22 WO 2007/041862 PCT/CA20061001686 obtained and to each was added 5.0 ml aliquots were obtained, and placed in 20 ml scintillation vials. To each was added dropwise with vigorous stirring 5.0 ml of aqueous Cd(NO 3

)

2 solutions of different concentrations (0.1 mM - 6.0 mM) yielding 10 mL of Cd 2 /PDDA solutions with different [Cd 2 ] between 0.1 mM and 3.0 mM 5 and a final PAA concentration of I mg/ml The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of Cd(NO 3

)

2 concentration changed suddenly at between I - 2 mM; this was taken as the PAA collapse point with Cd such that at lower concentrations, the PAA is primarily in an extended configuration. Addition of more Cd(N0 3

)

2 such that the final concentration 10 >2 mM caused a white precipitate to form. Solutions with a final concentration of 1.2 mM Cd(N0 3

)

2 and approx 0.7 mg/ml PAA were then prepared for use in subsequent examples below; this solution is referred to as Cd 2 /PAA in this work. Example 6: Polyanion collapse with (+3) cation. 15 In a 400 ml plastic beaker, 400.0 mg of poly(styrene sulfonic acid) (PSS) (Alfa Aesar, Average Mw I million) was dissolved in 200 ml deionized water. 5 ml aliquots of the PSS solution were obtained, and placed in 20 ml scintillation vials. To each was added dropwise with vigorous stirring 5.0 ml of aqueous solutions containting 20 FeC 3 of different concentrations (0.2 mM - 20.0 mM) yielding 10 mL of Fe 3 /PDDA solutions with different [Fe>3] between 0.1 mM and 10.0 mM and a final PSS concentration of 1 mg/mI. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of FeCI; concentration changed suddenly at approximately 2 mM; this was taken as the PSS collapse point with Fe3 25 such that at lower concentrations, the PSS is primarily in an extended configuration. Example 7: Polyanion collapse with 2 cations 30 In a 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 200 mi deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 * C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. pH measurements 35 were done using narrow range pH paper. 5.0 ml aliquots were obtained, and placed in 23 WO 2007/041862 PCT/CA2006/001686 20 ml scintillation vials. To each was added dropwise with vigorous stirring 5.0 ml of aqueous solutions containing FeCl 2 and LiCI at a mole ratio of (2:1) of different concentrations* (0.2 mM - 8.0 mM) yielding 10 mL of (2Fe 2t , Li')/PAA solutions with different [2Fe 2 , Li 2t ] between 0.1 mM and 4.0 mM and a final PAA 5 concentration of I mg/ml. The relative viscosity of each solution was measured with an Ostwald viscometer. The viscosity as a function of FeC12 and LiCl concentration changed suddenly at approximately 0.3 mM; this was taken as the PAA collapse point with 2Fe 2 , LiW such that at lower concentrations, the PAA is primarily in an extended configuration. 10 * concentrations refer to the total concentration of both metal ions combined Example 8; Preparation of Cd 2 +/PAA crosslinked composite nanoparticles according to the invention using mercury arc lamp 15 A solution of Cd 2 /PAA was prepared by dropwise addition of 10 ml of 0.005M Cd(N03) 2 solution to 10 ml of 2mg/ml aqueous solution of PAA (Sigma, Ave Mw 1.2 million PAA, pH adjusted to 6.8 with 0.1 M NaOH). The solution was exposed to light from a 200 W mercury arc lamp for approximately I hour to effect 20 collapse, while undergoing vigorous stirring. The irradiated solution was then dialyzed against deionized water for 3 hours. The dialysis is expected to substantially reduce the concentration of ions in solution, thus reversing the polymer collapse. However, it was found that the solution viscosity remains unchanged (still low), indicating that the collapsed configuration is retained, and that the collapsed polymer 25 has been crosslinked to remain in the collapsed configuration. An aliquot of the solution was cast onto mica and allowed to air dry. Atomic force microscopy imaging indicated the presence of particles 10 -25 nm in size. Example 9: Preparation of Zn 2 +/PAA and Cd7 t /PAA erosslinked composite 30 nanoparticles according to the invention using laser irradiation A solution of Zn'4/PAA was prepared by dropwise addition of 10 ml of 0.005M Zn(N0 3

)

2 solution to 10 ml of 2mg/ml aqueous solution of PAA (Sigma, Ave M 1.2 million PAA, pH adjusted to 6.8 with 0.1 M NaOH) with vigorous stirring. 35 The solution was exposed to 5000 pulses from an excimer laser source (1 OmJcm 3 ) while undergoing vigorous stirring. The laser irradiated solution was then dialyzed 24 WO 2007/041862 PCT/CA2006/001686 against deionized water for 3 hours, changing the deionized water reservoir every hour. The solution viscosity remained unchanged by dialysis, indicating that the collapsed configuration is retained. A solution of Cd 2 "/PAA was prepared by dropwise addition of 10 ml of 5 0.005M Cd(N0 3

)

2 solution to 10 ml of 2mg/ml aqueous solution of PAA (Sigma, Ave M. 1.2 million PAA, pH adjusted to 6.8 with 0.1 M NaOH) with vigorous stirring. The solution was exposed to 5000 pulses from an excimer laser source (lOmJ/cm 3 ) while undergoing vigorous stirring. The laser irradiated solution was then dialyzed against demonized water for 3 hours, changing the demonized water reservoir every 10 hour. The solution viscosity remained unchanged by dialysis, indicating that the collapsed configuration is retained. Example 10: Preparation of Zn 24 /PAA crosslinked composite nanoparticles according to the invention using chemical crosslinking agent 15 Zn 2 /PAA solution was prepared according to example 9. 2.0 ml of Zn 2 +/PAA was placed in a 5 ml glass vial and 160 [d of a solution that was 26.4mg/ml. in I Ethyi-N'(3-dimethylaminopropyl)carbodiimide (EDC) and 33.45 mM in 2,2' (Ethylenedioxy)bis-(ethylamine) (EDE) was added under constant stirring. The 20 resulting solution was stirred for 12 hours and was then dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. 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 EDC/EDE treated Zn 2 /PAA solution was much lower than that of an 25 untreated Zn 2 +/PAA solution. This indicates that the collapsed configuration is retained after Zn2+/PAA was treated with the EDC/EDE solution. Example 11: Polyacrylic acid crosslinking with gamma radiation to produce Cd 2 +/PAA composite nanoparticles according to the invention. 30 20 ml of Cd 2 /PAA, prepared as described in Example 5, was placed in a 20 ml scintillation vial. To this, 200 pi of isopropanol (ACS grade) was added. The vial was sealed with a rubber septum and was 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/hr. 35 The irradiated solution was then dialyzed against deionized water for 3 hours, 25 WO 2007/041862 PCT/CA2006/001686 changing the deionized water reservoir every hour. Similarly, Cd"/PAA that was not exposed to gamma radiation was also dialyzed in a similar manner. After dialysis, the viscosity of the collapsed irradiated, dialyzed solution was much lower than that of a collapsed, un-irradiated solution. Na-/PA A prepared according to example 4, [Na*]= 5 2mM, was also exposed to the same gamma radiation dose, and similarly the viscosity of the collapsed irradiated, dialyzed Na+/PAA solution was much lower than that of a collapsed, un-irradiated solution. Example 12: Polyacrylic acid crosslinking with 4 G25TS Germicidal lamps to 10 produce Cd 1 +/PAA composite nanoparticies according to the invention. 20 ml of Cd /PAA was prepared according to Example 5 was placed in a 50.0 ml glass beaker. The solution was exposed to 4 G25T8 germicidal UV lamps (approximate power is 12 gW/mm 2 ) for approximately 1.5 - 2 hours under vigorous 15 stirring. The irradiated solution was then dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. Cd 2 + PAA that was not exposed to the JV lamp was also dialyzed in a similar manner. The viscosity of the irradiated, dialyzed Cd 24 /PAA solution was much lower than that of a Cd 2 t /PAA solution that was not exposed to the UV lamp. Collapsed PAA with Zn(N0 3

)

2 , 20 Pb(NO 3 )z, Cd/Pb(NO 3

)

2 , Zn/Cd(NO 3

)

2 , FeCI 2 , LiCl, FeCU, Co(SO4). Cu(SO4), Mn(SO4), Ni(CH 3 COOH), Zn(N0 3

)

2 /MgC 2 was also UV irradiated in a similar manner and the viscosity of the collapsed irradiated, dialyzed solutions were much lower than that of a collapsed, un-irradiated solutions. These solutions were filterable using a 0.2 pm nylon syringe filter. 25 Example 13: CdS/PAA composite nanoparticles according to the invention. 20 ml of crosslinked Cd 2 /PAA composite nanoparticles was prepared according to example 12 and was placed in a 50 ml glass beaker. Under vigorous 30 stirring, 20.0 ml of 0.60 mM Na 2 S solution was added dropwise at a rate of 2 ml/min using a syringe pump. The resulting solution was yellow in color. 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 Na 2 S to the amount to Cd 2 ions present in the Cd2 4 /PAA solution. This is shown in 35 Figure 2. A red shift in the Emission,,, is observed as more Na 2 S is added. 26 WO 2007/041862 PCT/CA2006/001686 Scanning Transmission Electron microscopy images of the CdS/PAA prepared are shown in Figure 3. Example 14: CdSe/PAA Composite Nanoparticles according to the invention. 5 300 mL of Cd 2 /PAA was prepared according to Example 5. The pH of the solution adjusted to ~ 8.5 - 9.0 with 0.1 M NaOH and was bubbled with N(,) for 30 minutes in-a 500 ml round bottom flask. 18.2 mg of 1,I'- dimethylselenourea was dissolved in 5 ml of degassed, deionized water and was sealed with a septa in a 5 ml 10 glass vial. Using a 5 ml syringe, 4.1 ml of this dimethlyselenourea solution was added to the Cd /PAA under N 2 atmosphere. The resulting solution was stirred for 10 minutes and then heated on a heating mantle to a temperature of approximately 80C for 1 hour. After one hour, the solution was allowed to cool. The resulting solution has an absorption and emission spectra shown in Figure 4. 15 Example 15: (CdSe - CdS)/PAA Composite Nanoparticles according to the invention. 20 150 ml of CdSe/PAA nanoparticles produced according to Example 14 was placed in a 250 ml round bottom flask. 125.0 ml of 0.30 M Ihioacetamide in water was added to the flask containing the CdSe/PAA nanoparticles. The resulting mixture was stirred vigorously for 5 minutes, and was then heated to 80"C on a heating mantle with very light stirring for 24 hours. The absorption and emission spectra of the 25 resulting (CdSe-CdS)/PAA composite nanoparticles are shown in Figure 5. Example 16: CdTe/PAA Composite Nanoparticles according to the invention. 30 Under ambient conditions, 300 ml of Cd2 4 /PAA produced according to Example 5 was placed in a 500 ml round bottom flask. To this solution, 0.156 g of NaBH 4 and 0.312 g of trisodium citrate was added while the solution was being stirred. Immediately after the addition of the borohydride and the citrate, 12.5 ml of 0.0IM NaTeO 3 was added. Upon addition of the NaTeOj solution, the solution 35 develops a yellow color. The solution was then refluxed for approximately 20 hours 27 WO 2007/041862 PCT/CA2006/001686 to allow CdTe/PAA nanoparticles to form. The absorption and emission spectra of the resulting solution after 20 hours of reflux is shown in Figure 6. Example 17: (CdTe-ZnS)/PAA Composite Nanoparticles according to the 5 invention. In 50 a ml falcon tube, 1-7 ml of 3M NaCl was added to 15 ml CdTe/PAA nanoparticles particles formed according to Example 16. The resulting mixture was vortexed for 10 seconds after which 30 ml of absolute ethanol was added and was 10 centrifuged at 8500 rpm for 15 minutes. After centrifugation, the brown pellet formed at the bottom of the falcon tube was rinsed with 20ml 70 % ethanol. The resulting solution was centrifuged at 8500 rpm for 10mins. The brown pellet was isolated and resuspended in 15 ml deionized water. To 10 ml of the resuspended CdTe/PAA nanoparticles, 278 pL of 24mM Zn(NO 3

)

2 was added. The solution was stirred for 10 15 minutes after which 167 pL 39.5 mM Na 2 S was added. After 10 minutes of stirring, a second 278 jiL of 24mM Zn(N03)2 was added. The solution was stirred for 10 minutes after which 167 aL 39.5 mM Na 2 S was added. After 10 more minutes of stirring, a third 278 pL of 24mM Zn(NO3) 2 was added. The solution was stirred for 10 minutes after which 167 gL 39.5 mM Na 2 S was added. The solution was left in a 20 50 ml falcon tube for at least 3 days before taking the emission spectra. The resulting solution's absorption and emission spectra after 3 days is shown in Figure 7. Example 18: Formation of LiFePO4/PAA Composite Nanoparticles according to the invention. 25 A 20 ml solution of (Fe2+, Li*)/PAA was prepared according to Example 7 with some modifications. Briefly, in a 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1,2 million) was dissolved in 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 C) and was 30 stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled to room temperature, the pH was adjusted to 3.0 using 0.1 M HNO 3 , pH measurements were done using narrow range pH paper. 10.0 ml of this PAA solution was taken and placed in a 50 ml glass beaker to which 10.0 ml of a solution that was 6.7 mM in both FeCl 2 and LiC1 was added dropwise with vigorous 35 stirring. The solution was crosslinked for 1.5 hours under 4 G25T8 Germicidal 28 WO 2007/041862 PCT/CA2006/001686 lamps. 5.0 ml of a 13mM NILH 2 P0 4 was then added to the UV exposed (Fe, Li')/PAA. The solvent (water) of the resulting solution was removed using a rotary evaporator. When all of the solvent was removed, a light green colored residue remained and was then dried under vacuum for 12 hours. This light green residue was 5 placed in tube furnace and was heated under N 2 atmosphere for 12 hours at 600"C. After 12 hours of heating in the furnace, the light green residue tuned black. The STEM images with EDX analysis of the LiFePOVPAA composite nanoparticle are shown in Figure 8. Figure 8a is a STEM image of LiFePO 4 /PAA prepared according to the present invention, and wherein Figure 8b shows the cross-sectional abundance 10 of phosphorous along the scanned line in Figure 8a acquired using electron dispersive x-rays; and Figure Sc shows the cross-sectional abundance of iron along the scanned line in Figure 8a acquired using electron dispersive x-rays. The XRD pattern for the LiFePO 4 PAA composite nanoparticle is shown in Figure 9. 15 Example 19: Formation of Fe 2

O

3 /PAA Composite Nanoparticles according to the invention. Fe 2 OPAA is formed by 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 20 using 0-1M NaOH before adding the FeCl 2 and LiCI solution. The rest of the procedure remains the same. Surprisingly, this single modification leads to the formation of Fe 2

O

3 /PAA instead of LiFePO 4 /PAA. The STEM images with [DX analysis of the LiFePO 4 1PAA nanocomposite particles are shown in Figure 10. Figure 10a is a STEM image Fe 2

O

3 /PAA nanocomposite prepared according to the present 25 invention, and wherein Figure 10b shows the cross-sectional abundance of iron along the scanned line in Figure 10a acquired using electron dispersive x-rays; and Figure 10c shows the cross-sectional abundance of phosphorous along the scanned line in Figure 10a acquired using electron dispersive x-rays. The XRD pattern is shown in Figure 11, wherein H is hematite, alpha-Fe203 and M is defect spinal structure of 30 magnetite, gamma-Fe203, maghemite. Note that although the EDX images show the presence of phosphate, the XRD pattern suggests that Fe 2

O

3 is present and not LiFePO 4 . 29 WO 2007/041862 PCT/CA2006/001686 Example 20: Formation of ZnO/PAA Composites Nanoparticles according to the invention. A 20 nit solution of Zn 24 /PAA was prepared by dropwise addition of 10 ml of 5 0.005M Zn(NO3)2 solution to 10 ml of 2mg/ml aqueous solution of PAA (Sigma, Ave M" 1.2 million PAA, pH adjusted to 6.8 with 0.1 M4 NaOJ) with vigorous stirring. The solution was exposed to UV radiation for 1.5 hours under 4 G25T8 Germicidal lamps as in Example 12. The pH UV exposed Z 2 /PAA was adjusted to p-1 11.0 with 0.1 M NaOH, and then refluxed for I hour. After reflux, the solution turns 10 slightly cloudy. The absorbance, emission spectra and STEM image are shown in Figure 12 and the absorbance and emission spectra are shown in Figure 13. Example 21: Incorporation of CdS/PAA Composite Nanoparticles according to the invention into layer-by-layer thin films. 15 Polystyrene substrates were sonicated in 0.01M sodium dodecyl sulfate + 0.M HCI solution for 3 minutes, rinsed with distilled water, and dried with nitrogen. Layer by Layer (LbL) thin films were formed by immersing the substrate in 1mg/ml PAH (poly(allylamine) hydrochloride) in 0.lM NaCl for 5 minutes, followed by a 5 20 minute rinse in 0.IM NaCI, then immersed in a solution of CdS/PAA nanoparticle solution (prepared according Example 13) for 5 minutes, then rinsed in 0.1M NaCl solution for 5 minutes. This process was repeated 100 times. Emission spectra of the polystyrene substrate coated with the LbL thin films of PAH:CdS/PAA composite nanoparticles is shown in Figure 14. 25 Example 22: Ag/PAA Composite Nanoparticles according to the invention. 20 ml of Ag/PAA was made according to Example 4. Briefly, in a 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 30 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 "C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. pH measurements were done using narrow range pH paper. 10.0 ml of this PAA solution was placed in a 20 ml 35 scintillation vial and to this, 10 ml of 4.0 mM AgNO 3 solution was added drop wise under constant stirring. 0.5 mL of 2-propanol was added to the mixture. The final 30 WO 20071041862 PCT/CA2006/001686 solution volume was 20 mL The vials were sealed with rubber septa and subjected to 60Co irradiation using a gamma cell type G.C. 220 with a dose rate of 3.3 kGy/hr, at a total dose of 15 kWy. The UV-vis spectra and STEM images of the resulting Ag/PAA composite nanoparticles are shown in Figures 15 and 16, respectively. 5 Example 23: Au/PAA Composite Nanoparticles according to the invention. 20 ml of Au3+/PAA was made according to Example 4. Briefly, in a 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 10 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 * C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. pH measurements were done using narrow range pH paper. 10.0 ml of this PAA solution was placed in a 20 ml 15 scintillation vial, and to this 10 ml of 4.0 mM IAuCl 3 solution was added drop wise under constant stirring. 0.5 mL of 2 -propanol was added to the mixture. The final solution volume was 20 mL The vials were sealed with rubber septa and subjected to 60 Co irradiation using a gamma cell type G.C. 220 with a dose rate of 3.3 kGy/hr, at a total dose of 15 kGy. The UV-vis spectra and STEM images of the resulting Au/PAA 20 composite nanoparticles are shown in Figures 17 and 18, respectively. Example 24: (Au, Ag)/PAA Composite Nanoparticles according to the invention. 20 ml of (Ag t , Au 3 )/PAA was made according to Example 4. Briefly, in a 25 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90, C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOH. pH measurements were 30 done using narrow range pH paper. 10.0 ml of this PAA solution was placed in a 20 ml scintillation vial, and to this 5 ml of 4.0 mM HAuCI 3 solution was added drop wise under constant stirring. This was then followed by the drop wise addition of 5.0 ml 4 mM Ag(NO3), and finally the addition of 0.5 ml of 2-propanol. The final solution volume was 20 mL. The solution was exposed to 4 G25T8 germicidal UV lamps 31 WO 20071041862 PCT/CA2006/001686 (approximate power is 12 gW/mm 2 ) for approximately 1.5 - 2 hours under vigorous stirring. After irradiation, the solution changed from colorless to light purple. The UV-vis spectra and STEM images of the resulting (Au.Ag)/PAA composite nanoparticles are shown in Figures 19 and 20, respectively. Figure 20a is a STEM 5 image (Au, Ag)/PAA nanocomposite prepared according to the present invention; and wherein Figure 20b shows the cross-sectional abundance of silver along the scanned line in Figure 20a acquired using electron dispersive x-rays; and Figure 20c shows the cross-sectional abundance of gold along the scanned line in Figure 20a acquired using electron dispersive x-rays. 10 Example 25: Formation of CdSePAA-Fluorescein conjugate according to the invention. 15 In a 1.5 mL microfuge tube, 400 pL of CdSePAA (-0.2 mg/mL in ddH2O) was combined with 4.9 mg 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and 6 mg N-hydroxysuccinimide (NHS) in 500 ±L of ddH 2 0. 100 pL of 250 mM 2 morpholinoethanesulfonic acid (MES) (pH -6.5) was added. And finally, 20 gL of 5 mg/mL fluorescein in N,N-dimethylformamide (DMF) was also added. The tube 20 containing this mixture was wrapped in aluminum foil and placed on a rotating table for -20 h at room temperature. The resulting mix was placed in a 10 kDa MWCO dialysis bag and dialyzed against ddH 2 0. The dialysis solution (-200 fold dilution each time) was changed five times over a period of -24 h, The solution remaining in the dialysis bag was recovered and centrifuged for 10 min at 15,000 RCF, A brown 25 pellet is found after the centrifugation. The fluorescent supernatant was transferred to a new microfige tube and further purified by precipitation with the addition of-/10 volume of 3M sodium acetate (pH1 -5.5) and 2X volume of absolute ethanol. The resulting fluorescent precipitate was then isolated by centrifugation for 10 min at 15,000 RCF and suspended in 200 RL ddH 2 0. 30 The presence of 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 CdSePAA-BSA conjugate according to the invention. 32 WO 2007/041862 PCT/CA2006/001686 In a 1.5 mL microfuge tube, 900 pL of CdSe/PAA (-0.2 mg/mTL in ddH 2 O) was combined with 5.3 mg EDC and 10.8 mg NHS in 100 pL of 250 mM MES (pH 6.5). And finally, 5.1 mg bovine serum albumin (BSA) was also added. The tube 5 containing this mixture was placed on a rotating table for -19 h at room temperature. The resulting mix was centrifuged for 10 min at 15,000 RCF. -500 FL of the superatant was transferred to a 100 kDa NWCO centrifugal filter and centrifuged for 12 min at 14,000 RCF. The resulting filtrate was discarded, and the retenate was resuspended in 500 L of ddH 2 0 in the same filter and centrifuged again. This was 10 repeated three more times. The final retenate was recovered for characterization. Removal of unconjugated BSA using the 100 kDa MWCO filter was confirmed by gel penrication chromatography. And the presence of BSA conjugated to CdSe/PAA remaining in the retenate was confirmed by assay with BioRad protein reagent. 15 Example 27: CdS/PSS Composite Nanoparticles according to the invention. 400 mg of Poly(styrene sulfonic acid) sodium salt (Alfa Aesar, Ave M, I million) was dissolved in 200.0 ml deionized water. 20.0 ml of this solution was 20 placed in an 80 ml vial and to this, 20.0 mI 4.8 mM Cd(N0 3

)

2 solution was added dropwise with vigorous stirring. The solution was exposed to 4 G25T8 germicidal UV lamps (approximate UV power is 12 pW/mm 2 ) for I hour under vigorous stirring. US was formed by adding 0.5 ml 1.4 mM Na 2 S to 0.5 ml of the irradiated Cd2/PSS solution. UV-visible absorbance and emission spectra are shown in Figure 21. 25 Example 28: CdS/PDDA nanoparticles. 15.0 ml of poly(diallyidimethylammonium chloride) (PDDA) {Sigma, Average M" 400-500K, 20 wt% in water] was diluted to 300 ml with deionized water. The 30 solution was stirred for 10 minutes. 5.0 ml of this solution was diluted to 25.0 mil with deionized water in a 80 ml glass beaker. To this solution, 25.0 ml of 4mM Na 2 S was added dropwise with vigorous stirring. The solution was exposed to 4 G25T8 germicidal UV lamps (approximate UV power is 12 gW/mm 2 ) for I hour under vigorous stirring. CdS/PDDA was formed by adding 0.50ml of 2.68 mM Cd(N0 3

)

2 to 33 WO 20071041862 PCT/CA2006/001686 0.50 ml of irradiated S 2 -/PDDA. UV-visible absorbance and emission spectra are shown in figure 22. Example 29: Polyanion collapse with Cd'/Pb 2 cations 5 In a 400 mL plastic beaker, 400.0 mg of PAA (Sigma, Average Mv .2 million) was dissolved in 200 mL deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 "C) and was stirred vigorously for at least 30 minutes or until all of 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 10 were done using narrow-range pH paper. 25 mL of a CdPbl,(NO 3

)

2 solution was prepared by the addition of 5 mM Cd(N0 3

)

2 and 5 mM Pb(N0 3

)

2 salt solutions in various proportions, where x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,_ .L The total concentration of metal ions in the final solution was 5 mM. 20 mL of the pH-adjusted PAA and 25 mL of deionized water were obtained and placed in a 100 mL beaker. 15 mL of the 15 metal solution was then added dropwise under vigorous stirring to yield 60 mL of a Cd"PbtIPAA solution with a final [CdYPb_']of 1.25 mM and final PAA concentration of 0.67 mg/mL. Example 30: Polyanion collapse with Cd 2 t-Mg 2 (10%) cations 20 In a 400 mL plastic beaker, 400.0 rng of PAA (Sigma, Average Mv 1.2 million) was dissolved in 200 mL deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 "C) and was stirred vigorously for at least 30 minutes or until all of 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 25 were done using narrow-range pH paper. 25 mL of a CdocMg0,,(NO 3

)

2 solution was prepared by mixing together of 22.5 mL and 2.5 mL of 5 mM Cd(NO 3

)

2 and 5 mM Mg(NO3)2 solutions, respectively. The total concentration of metal ions in solution was 5 mM. 20 mL of the pH-adjusted PAA and 25 mL of deionized water were obtained and placed in a 100 rL beaker. 15 mL of the metal solution was then added 30 dropwise under vigorous stirring to yield 60 mL of a Cd Mg i /PAA solution with a final [CdjiMg "]of 1.25 mM and final PAA concentration of 0.67 mg/mL. 34 WO 2007/041862 PCT/CA2006/001686 Example 31: Polyanion collapse with Cd 2 +-Zn 2 +(90%) Cations In a 400 mL plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 200 mL deionized water. The plastic beaker was immersed 5 in a hot water bath (approximately 80-90 C) and was stirred vigorously for at least 30 minutes or until all of 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. pI measurements were done using narrow-range pH paper. 10 nL of a Cdo iZno, 9 (NO3) 2 solution was prepared by mixing together of 1 mL and 9 mL of 5 mM Cd(NO 3 )2 and 5 mM 10 Zn(N0 3

)

2 solutions, respectively. The total concentration of metal ions in solution was 5 mM, 10 mL of p1--adjusted PAA was obtained and placed in a 50 mL beaker followed by the dropwise addition of 10 mL of the metal salt solution under vigorous stirring to yield 20 mL of a Cd21Zn IPAA solution with a final (Cd,7Zn"]of 2.5 mM and final PAA concentration of I mg/mL. 15 Example 32: Polyanion collapse with Cd 2 -Zn4(10%) cations In a 400 mL plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 200 mL deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 C) and was stirred vigorously for at least 30 20 minutes or until all of the solid PAA had dissolved. Once the solution had cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOl. pH measurements were done using narrow-range pH paper. 6 mL of a Cdo 9 Zno1(NO 3

)

2 solution was prepared by mixing together of 5.4 mL and 0.6 mL of 5 mM Cd(NO 3

)

2 and 5 mM Zn(N03) 2 solutions, respectively. The total concentration of metal ions in solution 25 was 5 mM. 10 mL of pH-adjusted PAA and 4 mL of deionized water were obtained and placed in a 50 mL beaker, 6 mL of the metal salt solution was then added dropwise under vigorous stirring to yield 20 mL of a Cd.Zn, /PAA solution with a final [CdZnflof 1.5 mM and final PAA concentration of I mg/mL 30 Example 33: Polyanion collapse with Cd 2 /Mn'(l %) cations In a 400 mL plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1-2 million) was dissolved in 200 mL deionized water. The plastic beaker was immersed 35 WO 20071041862 PCT/CA2006/001686 in a hot water bath (approximately 80-90 *C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA had dissolved. Once the solution had cooled to room temperature, the plH was adjusted to 6.8 using 0.1 M NaOH. pH[ measurements were done using narrow-range pH paper. 25 mL of a Cdo.ggMnoo,(N0 3

)

2 solution was 5 prepared by mixing together of 24.75 ml. and 0.25 mL of 5 mM Cd(N0 3

)

2 and 5 mM Mn(NO 3

)

2 solutions, respectively. The total concentration of metal ions in solution was 5 mM. 20 mL of the pH-adjusted PAA and 25 mL of deionized water were obtained and placed in a 100 mL beaker. 15 mL of the metal solution was then added dropwise under vigorous stirring to yield 60 mL of a Cd-|Mn 1 / PAA solution with a 10 final [Cd Mno 1 jof 1.25 mM and final PAA concentration of 0.67 mg/mL. Example 34: Polyanion collapse with Cdt/Hg 2 ±(50%) cations In a 400 mL plastic beaker, 400.0 mg of PAA (Sigma, Average Mv 1.2 million) was dissolved in 200 mL deionized water. The plastic beaker was immersed 15 in a hot water bath (approximately 80-90 "C) and was stirred vigorously for at least 30 minutes or until all of 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 done using narrow-range pH paper. 25 ml, of a Cdo 0 sHgo.5(N0 3

)

2 solution was prepared by mixing together of 12.5 mL and 12.5 mL of 5 mM Cd(NO 3

)

2 and 5 mM 20 Hg(NO3)2 solutions, respectively. The total concentration of metal ions in solution was 5 mM. 20 mL of the pH-adjusted PAA and 25 mL of deionized water were obtained and placed in a 100 mL beaker. 15 mL of the metal solution was then added dropwise under vigorous stirring to yield 60 mL of a CdHgJ; / PAA solution with a final [Cd 0 2 Hgn ]of 1.25 mM and final PAA concentration of 0.67 mg/mL. 25 Example 35: Polyacrylic acid crosslinking with 4 G25TS germicidal lamps 60 mL of Cd'+Pb'_ / PAA was prepared according to Example 29 and was placed in a 150.0 mL glass beaker. The solution was exposed to 4 G25T8 germicidal UV lamps (approximate power is 12 pW/mm 2 ) for approximately 30 minutes under 30 vigorous stirring. The irradiated solution was then dialyzed against deionized water for 3 hours, changing the deionized water reservoir every hour. Collapsed PAA with 36 WO 2007/041862 PCT/CA2006/001686 CdZn 1 x(NO3) 2 , CdxMni,(NO 3

)

2 , CdMgi.(NO 3

)

2 ... was UV-irradiated in a similar manner for approximately I hour. The viscosity of the collapsed irradiated, dialyzed solutions was much lower than that of collapsed, un-irradiated solutions. These solutions were filterable using a 0.2 pm nylon syringe filter. 5 Example 36: Cdo.sPbo.sTe/PAA nanoparticles Under ambient conditions, 20 ml of Cd"Pb / PAA produced according to Example 29 was placed in a 100 mL round bottom flask. The piH was adjusted to II 10 using 1.1 M NaOH4. pH measurements were done using narrow-range pH paper. To this solution, 20.4 mg of NaBH 4 and 28.3 mg of trisodium citrate were added while the solution was being stirred. Immediately after the addition of the borohydride and the citrate, 0.625 mL of 0.01 Na 2 TeO 3 was added. The solution develops a yellow colour upon addition of the tellurium-containing salt. The solution was then refluxed 15 for approximately one hour under N2 atmosphere to allow CdPbTe/PAA nanoparticles to form. The absorbance and emission spectra of the resulting solution after one hour of reflux is shown in Figure 23. Unfortunately, the colloidal solutions were extremely unstable upon exposure to air and this was marked by a quick disappearance of the characteristic absorbance and emission spectra shown in Figure 20 23. Example 37: CdosZnoaTe/PAA nanoparticles Under ambient conditions, 8 mL of CdlZn27 /PAA produced according to Example 32 was placed in a 25 mL round bottom flask, and cross-linked using the 25 permitted lamp as hereinabove described. To this solution, 15 mg of NaBH 4 and 30 mg of trisodium citrate were added while the solution was being stirred. Immediately after the addition of the borohydride and the citrate, 0.3 mL of 0.01 Na2TeO 3 was added. The solution develops a peach colour upon addition of the tellurium containing salt. The solution was then refluxed for approximately two hours to allow 30 CdZnTe/PAAnanoparticles to form. The absorbance and emission spectra of the resulting solution after two hours of reflux are shown in Figure 24. 37 WO 20071041862 PCT/CA2006/001686 Example 38; Cdrj9Mno.otTe/PAA nanoparticles Under ambient conditions, 10 mL of Cd74,Mn, /PAA produced according to Example 33 was placed in a 25 mL round bottom flask, and cross-linked using the permitted lamp as hereinabove described. To this solution, 20 mg of NaBH4 and 37 5 mg of trisodium citrate were added while the solution was being stirred. Immediately after the addition of the borohydride and the citrate, 0.313 mL of 0.01 Na 2 TeO 3 was added. The solution develops a peach colour upon addition of the tellurium containing salt. The solution was then refluxed for approximately one hour to allow CdMnTe/PAA nanoparticles to form. The absorbance and emission spectra of the 10 resulting solution after one hour of reflux are shown in Figure 25. Example 39: Cdo.sHgoasTe[PAA nanoparticles Under ambient conditions, 10 mL of CdJHgh /PAAproduced according to Example 34 was placed in a 25 mL round bottom flask, and cross-linked using the 15 permitted lamp as hereinabove described. To this solution, 16 mg of NaBH4 and 29 mg of trisodium citrate were added while the solution was being stirred. Immediately after the addition of the borohydride and the citrate, 0.3 [3 mL of 0.01 Na 2 TeO 3 was added. The solution remained colourless upon addition of the tellurium-containing salt. The solution was then refluxed for approximately one hour to allow 20 CdHgTe/PAA nanoparticles to form. However, the refluxed solution was not fluorescent. Example 40: Fomation of Methylene Blue/PAA nanoparticles In a 400 ml plastic beaker, 400.0 mg of PAA (Sigma, Average My 1.2 million) 25 was dissolved in 200 ml deionized water. The plastic beaker was immersed in a hot water bath (approximately 80-90 " C) and was stirred vigorously for at least 30 minutes or until all of the solid PAA has dissolved. Once the solution has cooled to room temperature, the pH was adjusted to 6.8 using 0.1 M NaOl . pH measurements were done using narrow range pH paper. 20.0 ml of this PAA solution was placed in 30 a glass beaker and to this, 20.0 ml of aqueous 5.0 mM Methylene Blue solution was added dropwise under vigorous stirring. After all of the Methylene Blue solution was added, the viscosity of the mixture was observed to be much less than the original 38 PAA solution. The resulting solution was exposed to UV radiation using 4 G25T8 germicidal UV lamps for 1.5 hours. The viscosity of the UV-irradiated Methylene Blue/PAA solution was less than the viscosity of the solution not exposed to UV radiation. 5 All literature and similar material cited in this application, including, patents, patent applications, articles, books, treatises, dissertations and web pages, regardless of the format of such literature and similar materials, are expressly incorporated by reference in their entirety. In the event that one or more of the incorporated literature and similar materials differs from or contradicts this application, including defined terms, term usage, described techniques, or the 10 like, this application controls. The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described in any way. While the present inventions have been described in conjunction with various embodiments and examples, it is not intended that the present inventions be limited to such 15 embodiments or examples. On the contrary, the present inventions encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art. Accordingly, the descriptions, methods and diagrams of should not be read as limited to the described order of elements unless stated to that effect. Although this disclosure has described and illustrated certain preferred embodiments of 20 the invention, it is to be understood that the invention is not restricted to those particular embodiments. Rather, the invention includes all embodiments which are functional or mechanical equivalence of the specific embodiments and features that have been described and illustrated. The claims should not be read as limited to the described order or elements unless 25 stated to that effect. 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 embodiments that come within the scope and spirit of the following claims and equivalents thereto are claimed. Throughout this specification and the claims which follow, unless the context requires 30 otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common 35 general knowledge in Australia. 39

Claims (57)

1. A method for producing a composite nanoparticle, comprising the steps of: collapsing at least a portion of a polyclectrolyte polymer material in solution about one or more precursor moieties to form a composite precursor moiety having a mean diameter in the range between about 1 nm and about 100 nm, wherein the polyelectrolyte polymer material has an extended conformation in a first solution state and a more compact conformation in a second solution state; and cross-linking the polyelectrolyte polymer material of said composite precursor moiety to form a composite nanoparticle.

2. The method of claim 1, wherein the composite nanoparticle has a mean diameter in the range between about 1 nm and about 100 nm.

3. The method of claim 1, wherein the collapsing step comprises adding a collapsing agent to the polymeric solution.

4. The method of claim 3, wherein the precursor moiety is a collapsing agent.

5. The method of claim 4, wherein the collapsing agent comprises at least one ionic species.

6. The method of claim 5, wherein the ionic species comprises one or more inorganic salts, organic salts, or combination thereof

7. The method of claim 1, further comprising exposing the composite precursor moiety to electromagnetic radiation to form the composite nanoparticle.

8. The method of claim 1, further comprising subjecting the composite nanoparticle to a chemical treatment. 40

9. The method of claim 8, wherein the chemical treatment results in a reduction or oxidation of the composite nanoparticle.

10. The method of claim 8, wherein the chemical treatment comprises addition of a counter ion, or a precursor of the counter ion, to a precursor moiety of a composite nanoparticle.

11. The method of claim 1, wherein the solution is aqueous.

12. The method of claim 1, wherein the precursor moiety is selected from the group consisting of a metal cation, a metal anion, complexed metal cation, complexed metal anion and combinations thereof.

13. The method of claim 12, wherein at least a portion of the precursor moiety comprises two or more different metals; and wherein the nanoparticle formed comprises an alloy of two or more of the two or more metals.

14. The method of claim 1, wherein the polyelectrolyte polymer material comprises linear or branched segments comprising polyions, the polyions comprising one or more anions, cations, or combinations thereof.

15. The method of claim 1, wherein said polyelectrolyte polymer material comprises one or more functional groups.

16. The method of claim 1 wherein the polyelectrolyte polymer material is selected from the group consisting of poly(acrylic acid), poly(diallyldimethylammonium chloride), poly(styrene sulfonate), poly(ethyleneimine), poly(allylamine hydrochloride) and combinations thereof

17. The method of claim I wherein the polyelectrolyte polymer material comprises a plurality of molecules. 41

18. A method comprising the steps of: collapsing at least a portion of a polyelectrolyte polymer material in solution about one or more precursor moieties to form a composite precursor moiety having a mean diameter in the range between about 1 nm and about 100 nm, wherein the polyelectrolyte polymer material has an extended conformation in a first solution state and a more compact conformation in a second solution state; and cross-linking the first polyelectrolyte polymer material of said first composite precursor moiety to form a composite nanoparticle material; and contacting a substrate with at least a portion of the composite nanoparticle material to form a first layer on at least a portion of the substrate.

19. The method of claim 18, further comprising contacting at least a portion of the first layer with solution containing a charged compound to form a second layer, the charged compound having a charge substantially opposite to that of the composite nanoparticle material.

20. The method of claim 18, further comprising contacting the substrate with at least a portion of a second material to form a second layer on at least a portion of the first layer.

21. The method of claim 20, further comprising contacting the substrate with a charged compound, between contacting the substrate with either the composite nanoparticle material or the second material, wherein the charged compound has a charge opposite that of the previously contacted material.

22. The method of claim 20, wherein the second material is prepared by a method comprising the steps of collapsing at least a portion of a second polyelectrolyte polymer material about one or more second precursor moieties to form a second composite precursor moiety having a mean diameter in the range between about 1 nm and about 100 nm; and cross-linking the second polyelectrolyte polymer material of said second composite precursor moiety to form a second composite nanoparticle material. 42

23. The method of claim 22, wherein the first composite nanoparticle material and the second composite nanoparticle material are in the same solution.

24. The method of claim 18, wherein the substrate is a thin film.

25. The method of claim 19 wherein the charged compound comprises poly(allylamine).

26. The method of claim 18, wherein one or more of the layers on the substrate form an optically active material.

27. A method for producing a composite nanoparticle, comprising the steps of: collapsing at least a portion of a polyelectrolyte polymer material in solution about one or more precursor moieties to form a composite precursor moiety having a mean diameter in the range between about 1 nm and about 100 nm, wherein the polyelectrolyte polymer material has an extended conformation in a first solution state and a more compact conformation in a second solution state; and irradiating the polyelectrolyte polymer material of the composite precursor moiety with ionizing radiation to form a composite nanoparticle.

28. The method of claim 27, wherein the composite nanoparticle has a mean diameter in the range between about I nm and about 100 nn.

29. The method of claim 27, wherein the collapsing step comprises adding a collapsing agent to the polyelectrolyte polymer solution.

30. The method of claim 29, wherein the precursor moiety is a collapsing agent.

31. The method of claim 30, wherein the collapsing agent comprises at least one ionic species. 43

32. The method of claim 3 1, wherein the ionic species comprises one or more inorganic salts, organic salts, or combination thereof

33. The method of claim 27, further comprising subjecting the composite nanoparticle to a chemical treatment.

34. The method of claim 33, wherein the chemical treatment results in a reduction or oxidation of the composite nanoparticle.

35. The method of claim 33, wherein the chemical treatment comprises addition of a counter ion, or precursor of the counter ion, to a precursor moiety of a composite nanoparticle.

36. The method of claim 27, wherein the solution is aqueous.

37. The method of claim 27, wherein the precursor moiety is selected from the group consisting of a metal cation, a metal anion, complexed metal cation, complexed metal anion and combinations thereof.

38. The method of claim 37, wherein at least a portion of the precursor moiety comprises two or more different metals; and wherein the nanoparticle formed comprises an alloy of two or more of the two or more metals.

39. The method of claim 27, wherein the polymeric material comprises linear or branched segments comprising polyions, the polyions comprising one or more anions, cations, or combinations thereof.

40. The method of claim 27, wherein said polyelectrolyte polymer material comprises one or more functional groups.

41. The method of claim 27, wherein the polyelectrolyte polymer material is selected from the group consisting of poly(acrylic acid), poly(diallyldimethylammonium chloride), 44 poly(styrene sulfonate), poly(ethyleneimine), poly(allylamine hydrochloride) and combinations thereof

42. The method of claim 27, wherein the polyelectrolyte polymer material comprises a plurality of molecules.

43. The method of claim 1, wherein the collapsing is accomplished by changing the solution from a first solution state to a second solution state.

44. The method of claim 18, wherein the collapsing is accomplished by changing the solution from a first solution state to a second solution state.

45. The method of claim 27, wherein the collapsing is accomplished by changing the solution from a first solution state to a second solution state.

46. The method of claim 1, wherein the precursor moiety is an organic charged ion.

47. The method of claim 18, wherein the precursor moiety is an organic charged ion.

48. The method of claim 27, wherein the precursor moiety is an organic charged ion.

49. A composite nanoparticle comprising a nanoparticle confined within a cross linked collapsed polyelectrolyte polymer wherein the nanoparticle comprises a charged organic ion.

50. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about 1 nm to about 100 nm.

51. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about I nm to about 50 nm. 45

52. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about I nm to about 10 rnm.

53. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about 10 nm to about 30 nm.

54. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about 15 nm to about 50 rnm.

55. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about 50 nm to about 100 nm.

56. The composite nanoparticle of claim 49, wherein the composite nanoparticle has a diameter in the range of about 0.1 nm to about 100 nm.

57. The composite nanoparticle of claim 49, wherein the polyelectrolyte polymer is a copolymer. 46