# Patent

## Title
Encapsulated nanoparticles

## Abstract

In various embodiments, the present invention relates to production of encapsulated nanoparticles by dispersing said nanoparticles and an encapsulating medium in a common solvent to form a first solution system and applying a stimulus to said first solution system to induce simultaneous aggregation of the nanoparticles and the encapsulating medium.

## Background
RELATED APPLICATIONS
This application claims the benefit of and priority to application GB 1005601.8 filed Apr. 1, 2010 and U.S. Provisional Patent Application Ser. No. 61/320,924 filed Apr. 5, 2010, the disclosures of which are incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
In various embodiments, the present invention relates to a method for producing encapsulated nanoparticles and encapsulated nanoparticles per se. Embodiments relate particularly, but not exclusively, to polymer-encapsulated core and core/(multi)shell quantum dots which, as a result of their encapsulation, may be utilised in a wide range of applications, including biolabeling, biosensing, coding, biological monitoring, security optical coding, biological assays, solid-state lighting, optical data storage, sensors, and anti-counterfeiting.
BACKGROUND
Fluorescent dye-containing beads have been used for many years in diagnostics testing, microscope- and flow-cytometry-based assays, and combinatorial library synthesis. As such they can be routinely manufactured with a variety of surface modifications which enable many classes of molecules to be coupled and subsequently read and manipulated using commercially available instrumentation. The fluorescent organic dye molecules suffer from a number of disadvantages however including photo-bleaching, different excitation irradiation frequencies and broad emissions. Alternatives to conventional fluorescent materials have therefore been investigated. The substitution of the fluorescent organic molecules with luminescent compound semiconductor nanoparticles or “quantum dots” (QDs) is one approach which is intended to circumvent many of these limitations.
The size of a QD dictates the electronic properties of the material; the band-gap energy being inversely proportional to the size of the QDs as a consequence of quantum-confinement effects. Different sized QDs may be excited by irradiation with a single wavelength of light to give a discrete fluorescence emission of narrow band width. Further, the large surface-area-to-volume ratio of the QDs has a profound impact upon the physical and chemical properties of the QD.
Nanoparticles that comprise a single semiconductor material usually have modest physical/chemical stability and consequently relatively low fluorescence quantum efficiencies. These low quantum efficiencies arise from non-radiative electron-hole recombinations that occur at defects and dangling bonds at the surface of the nanoparticle.
Core-shell nanoparticles comprise a semiconductor core with a shell material of typically wider band-gap and similar lattice dimensions grown epitaxially on the surface of the core. The shell eliminates defects and dangling bonds from the surface of the core, which confines charge carriers within the core and away from surface states that may function as centres for non-radiative recombination. More recently, the architecture of semiconductor nanoparticles has been further developed to include core/multishell nanoparticles in which the core semiconductor material is provided with two or more shell layers to further enhance the physical, chemical and/or optical properties of the nanoparticles. To add further stability, a compositionally graded alloy layer can be grown epitaxially on to the nanoparticle core to alleviate lattice strain between adjacent layers that could otherwise lead to defects and reduce the photoluminescence (PL) emission of the QDs. The emission and absorption properties of the QDs can also be manipulated by doping wide band-gap materials with certain metals or luminescence activators to further tune the PL and electroluminescence (EL) at energies even lower than the band gap of the bulk semiconductor material, whereas the quantum size effect can be exploited to tune the excitation energy by varying the size of the QDs without having a significant effect on the energy of the activator-related emission.
The surfaces of core and core/(multi)shell semiconductor nanoparticles often possess highly reactive dangling bonds, which can be passivated by coordination of a suitable ligand, such as an organic ligand compound. The ligand compound is typically either dissolved in an inert solvent or employed as the solvent in the nanoparticle core growth and/or shelling procedures that are used to synthesise the QDs. Either way, the ligand compound chelates the surface of the QD by donating lone pair electrons to the surface metal atoms, which inhibits aggregation of the particles, protects the particle from its surrounding chemical environment, provides electronic stabilisation and can impart solubility in relatively non-polar media.
Various methods have been developed to try to incorporate QDs into beads in the form of resins, polymers, monoliths, glasses, sol gels, silicones, acrylates and other media. The term “beads” is used simply for convenience and is not intended to impose any particular shape or size limitation or composition. It relates to a solid-state medium of any three-dimensional shape of any size and of any composition. For example, beads may be spherical but other configurations are also contemplated.
One of the approaches to incorporating QDs into beads that has been investigated significantly to-date involves pre-coating the QDs with specific types of ligands, which are either polymerisable or compatible with the intended encapsulating polymer. Examples of polymerisation methods that may be used to construct QD-containing beads include suspension, dispersion, emulsion, living, anionic, cationic, RAFT, ATRP, bulk, ring closing metathesis and ring opening metathesis. Initiation of the polymerisation reaction may be caused by any appropriate technique, including free radicals, light, ultrasound, cations, anions, or heat. Examples of polymer-compatible QD surface ligands include ligands that may be hydrophobic, hydrophilic, positively or negatively charged, or functionalised with a reactive group capable of associating with the encapsulating polymer by chemical reaction, covalent linkage, or non-covalent interaction (intercelation). In an alternative approach, QDs have been immobilised in polymer beads through physical entrapment. A solution of QDs in an organic solvent is incubated with a sample of polymer beads. The solvent is then removed, resulting in the QDs becoming immobilised within the matrix of the polymer beads at which point the beads typically require some form of sealing procedure to be carried out to ensure the QDs remain immobilised within the beads. Unfortunately, while progress has been made, most of the approaches currently being investigated to encapsulate nanoparticles require processing steps which can be damaging to the integrity and/or optical performance of the QDs.
SUMMARY
Various embodiments of the present invention obviate or mitigate one or more of the problems currently associated with the production of encapsulated semiconductor nanoparticles. As used herein unless otherwise indicated, the term “approximately” means ±10%, and, in some embodiments, ±5%.
According to a first aspect, embodiments of the present invention feature a method for producing encapsulated nanoparticles including dispersing a plurality of nanoparticles and an encapsulating medium in a common solvent to form a first solution system and treatment of said first solution system with a stimulus suitable to induce simultaneous aggregation of the nanoparticles and the encapsulating medium. By “common solvent” is meant a single liquid medium in which both the nanoparticles and encapsulating medium are dispersed. The common solvent may consist of a single substance or may be a combination of multiple solvents.
Embodiments of the invention may include one or more of the following, in any of a variety of combinations. The treatment may destablise the first solution system so as to induce the simultaneous aggregation. The stimulus may include or consist essentially of a physical change to the first solution system (e.g., a change in temperature) resulting in simultaneous aggregation of the nanoparticles and the encapsulating medium. The stimulus may include or consist essentially of a chemical change to the first solution system (e.g., changing the pH of the first solution system, addition of a salting-out agent to the first solution system, and/or addition of a chaotropic agent) resulting in simultaneous aggregation of the nanoparticles and the encapsulating medium.
The chemical change may include or consist essentially of contacting the first solution system with a second solution system of different polarity and/or chemical composition than that of the first solution system. The first solution system may be introduced into the second solution system, or the second solution system may be introduced into the first solution system. The second solution system may include or consist essentially of a surfactant-type species or a non-surfactant. The second solution system may include or consist essentially of an aqueous solution of methyl cellulose, an aqueous solution of polyethyleneglycol, silicone oil, and/or acetylnitrile. The second solution system may include or consist essentially of a polarity-modifying agent. The polarity-modifying agent may decrease or increase the difference in polarity between the first and second solution systems, may be miscible in water, and/or may have a polarity index of approximately 4. The polarity-modifying agent may include or consist essentially of dioxane, acetonitrile, n-propanol, iso-propanol, and/or methyl ethyl ketone.
After contacting the first and second solution systems for a suitable period of time to induce simultaneous aggregation of the nanoparticles and the encapsulating medium, the common solvent may be removed and the encapsulated nanoparticles may be isolated. The nanoparticles may be combined with the encapsulating medium and the common solvent in the presence of an additive (e.g., a fatty acid, a saccharide, and/or an antioxidant) to stabilise the nanoparticles within the first solution system. The common solvent may include or consist essentially of an organic solvent. After aggregation of the nanoparticles and the encapsulating medium, the aggregate may be subjected to a further treatment step to improve the physical characteristics of the aggregate. For example, when the encapsulating medium includes or consists essentially of an epoxy, the further treatment step may include or consist essentially of crosslinking of the epoxy encapsulating medium.
The encapsulating medium may include or consist essentially of a polymeric encapsulating medium such as an organic polymer, an inorganic polymer, a water-soluble polymer, an organic-solvent-soluble polymer, a biological polymer, and/or a synthetic polymer. The encapsulating medium may include or consist essentially of a polymeric encapsulating medium such as polyacrylate, polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde, polystyrene, polyethylene, polypropylene, poly ketone, polyether ether ketone, polyester, polyamide, polyimide, polyacrylamide, polyolefine, polyacetylene, polyisoprene, polybutadiene, poly(vinylidene fluoride), poly(vinyl chloride), ethylene vinyl acetate, polyethylenetelephthalate, polyurethane, and/or a cellulose polymer. The encapsulating medium may include or consist essentially of a polymeric encapsulating medium such as a crosslinked or crosslinkable polymer, a crosslinked or crosslinkable copolymer, a triblock copolymer, a UV-curable epoxy polymer, and/or a thermally curable epoxy polymer. The encapsulating medium may include or consist essentially of a polymeric encapsulating medium such as polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde, polybutadiene, polyisoprene, polyethylene, and/or epoxy.
The encapsulating medium may include or consist essentially of bentonite, kaolin, fumed silica, fumed alumina, and/or fumed zinc oxide. The encapsulating medium may be optically transparent. The nanoparticles may include or consist essentially of semiconductor nanoparticles.
According to a second aspect, embodiments of the present invention feature encapsulated nanoparticles produced using methods in accordance with above-described embodiments of the present invention.



BRIEF DESCRIPTION OF THE FIGURES
Embodiments of the present invention are illustrated with reference to the following non-limiting figures in which:
FIG. 1 is a schematic illustration of a QD surrounded by an amine capping agent;
FIG. 2 is a schematic illustration of core, core/shell, and core/multishell QDs, each with an amine capping agent;
FIG. 3 is a schematic representation of a preferred embodiment of a method according to an aspect of the present invention;
FIG. 4 is a schematic representation of a preferred embodiment of a process according to an aspect of the present invention in which different coloured QDs are dispersed separately in polymer beads to produce a variety of beads of a single colour, and which are then combined in any desirable ratio in a single larger polymer bead such that the larger bead is of a desired colour;
FIG. 5 is a fluorescence microscopy image of QD-containing polystyrene beads (diameter of approximately 5 micron) contained within larger polycarbonate beads (diameter of approximately 50 micron) produced using a method according to a preferred embodiment of an aspect of the present invention;
FIG. 6 is a graph comparing the stability of two samples of QDs encapsulated in polycarbonate beads;
FIGS. 7a and 7b are microscopic images (at 1000× magnification) of polycarbonate beads containing QDs which have been made in the presence (FIG. 7a; refer to Example 8) and absence (FIG. 7b; refer to Example 7) of 20% THF in the outer (methyl cellulose) phase; and
FIG. 8 is a microscopic image (at 1000× magnification) of poly(o-cresylglycidylether)-co-formaldehyde beads containing QDs which have been made in the presence of 20% THF in the outer (methyl cellulose) phase (refer to Example 9).



DETAILED DESCRIPTION
Various embodiments of the present invention relate to the incorporation of nanoparticles, including for example, QDs, colloidal gold, colloidal silver, metal oxides etc., into an encapsulating medium which is preferably optically transparent, and is most preferably optically clear. It is preferred that the encapsulating medium is physically and chemically stable and sufficiently robust to withstand the conditions to which the resulting QD-containing beads will be subjected during their intended application.
In preferred embodiments of the method of the present invention the method may be separated into two fundamental stages. In a first stage, a solution system including or consisting essentially of the nanoparticles and the intended encapsulating medium (e.g., the encapsulating polymer) is formed using a common solvent that may uniformly disperse or dissolve both the nanoparticles and the encapsulant. In a second stage, the nanoparticle/encapsulant solution system is treated so as to undergo a physical and/or chemical change resulting in simultaneous aggregation of the nanoparticles and the encapsulating medium.
The treatment effected in the second step may involve contacting of the initial nanoparticle/encapsulant solution system with another solvent system possessing different polarity which destabilizes the initial solution system and induces the formation of nanoparticle/encapsulant aggregates. By way of further example, the second step may include a chemical change such as a change in pH, addition of a salting-out agent (e.g., an electrolyte such as sodium sulfate), or addition of a chaotropic agent (i.e., an agent which disrupts the structure of the nanoparticle/encapsulant solution system by interfering with intra-molecular interactions mediated by non-covalent forces which stabilise the initial solution system). Additionally or instead, the second step may involve a physical change, such as a change in temperature of the nanoparticle/encapsulant solution system.
The resulting material is an ensemble of aggregated beads that include or consist essentially of both the nanoparticles and the encapsulant. By changing the ratio and sequence of additions of the first and second systems, the size, loading ratio and uniformity of the encapsulating particles, e.g., beads, may be controlled. In an optional further step, the beads may be rigidized chemically and/or physically by solvent removal (de-solvation) and/or additional crosslinking to form self-supporting beads.
Producing QD-containing beads using embodiments of the present invention generally has the advantage of very little loss of quantum yield during processing as a result of using relatively mild conditions. Other advantages typically include the ability to produce beads with a high loading of nanoparticles and the ability to easily and conveniently scale-up production to large, commercially relevant volumes.
Methods sharing certain features with embodiments of the present invention have been developed previously for encapsulating small organic molecules, such as drug and dye molecules. Drug encapsulation has been investigated for various reasons including controlled release and minimizing unwanted side effects. Encapsulation of dye molecules has been used, for example, in the preparation of “carbonless paper.” These methods are, however, tailored specifically for the encapsulation of relatively small organic molecules which are quite distinct from the present invention which relates to the encapsulation of significantly larger nanoparticles, particularly, but not exclusively, inorganic compound semiconductor nanoparticles or QDs, which exhibit tunable luminescent properties. Smaller organic molecules will typically dissolve in a wider range of solvents than much larger inorganic materials, and molecules such as drug or dye molecules tend to form more stable colloidal dispersions more easily than nanoparticle-sized inorganic materials. As a result, it will be evident to the skilled person that the physical and chemical requirements of the common solvent used to disperse the nanoparticles and polymeric encapsulating medium to form the first solution system will be different to those of a solvent used to disperse a small organic molecule and its intended encapsulating medium. Moreover, the types of stimuli that may be appropriate to induce simultaneous aggregation of a population of nanoparticles and an encapsulating medium would be entirely different from those used if the nanoparticles were replaced with much smaller organic molecules. As such, it is not possible to derive any teaching or suggestion as to how to put into effect the method of the present invention from prior art methods of encapsulating small organic molecules.
The nanoparticles may be semiconductor nanoparticles, colloidal metal (e.g., Au or Ag) nanoparticles or metal oxide materials. Preferably the nanoparticles are luminescent compound-semiconductor nanoparticles or QDs. The nanoparticles may incorporate a core including a semiconductor material, preferably a luminescent semiconductor material. The semiconductor material may incorporate ions from any one or more of groups 2 to 16 of the periodic table, including binary, ternary and quaternary materials, that is, materials incorporating two, three or four different ions respectively. By way of example, the nanoparticles may incorporate a core semiconductor material, such as, but not limited to, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge and combinations thereof. Nanoparticles according to embodiments of the present invention preferably possess cores with mean diameters of less than approximately 20 nm, more preferably less than approximately 15 nm and most preferably in the range of approximately 2 to 5 nm.
Nanoparticles that include a single semiconductor material, e.g., CdS, CdSe, ZnS, ZnSe, InP, GaN, etc. usually have relatively low quantum efficiencies arising from non-radiative electron-hole recombinations that occur at defects and dangling bonds at the surface of the nanoparticles. In order to at least partially address these issues, the nanoparticle cores may be at least partially coated with one or more layers (also referred to herein as “shells”) of a different material to the core, for example a semiconductor material. The material included in the or each shell may incorporate ions from any one or more of groups 2 to 16 of the periodic table. Where a nanoparticle includes two or more shells, each shell is preferably formed of a different material. In an exemplary core/shell material, the core is formed of one of the materials specified above and the shell includes a semiconductor material of larger band-gap energy and similar lattice dimensions to the core material. Example shell materials include, but are not limited to, ZnS, MgS, MgSe, MgTe, GaN and metal oxides, such as ZnO, Fe2O3 and Fe3O4. The confinement of charge carriers within the core and away from surface states generally provides QDs of greater stability and higher quantum yield.
The mean diameter of the nanoparticles may be varied to modify the emission wavelength. The energy levels and hence the frequency of the nanoparticle fluorescence emission may be controlled by the material from which the nanoparticles are made and the size of the nanoparticles. Generally, nanoparticles made of the same material have a more pronounced red emission the larger the nanoparticle. It is preferred that the nanoparticles have mean diameters of approximately 1 to 15 nm, more preferably approximately 1 to 10 nm. The nanoparticles preferably emit light having a wavelength of approximately 400 to 900 nm, more preferably approximately 400 to 700 nm.
The coordination layer around the final inorganic surface atoms in any core, core-shell or core-multi shell, doped or graded nanoparticle is incomplete; with highly reactive non-fully coordinated atoms “dangling bonds” on the surface of the particle, which may lead to particle agglomeration. This problem is overcome by passivating (capping) the “bare” surface atoms with protecting organic groups. The outermost layer (capping agent) of organic material or sheath material helps to inhibit particle-particle aggregation and also further protects the nanoparticle from their surrounding electronic and chemical environments and it also provides a means of chemical linkage to other inorganic, organic or biological material. In many cases, the capping agent is the solvent that the nanoparticle preparation is undertaken in, and includes or consists essentially of a Lewis base compound, or a Lewis base compound diluted in an inert solvent such as a hydrocarbon. There is a lone pair of electrons on the Lewis base capping agent that is capable of donor-type coordination to the surface of the nanoparticle. Examples of such capping agents include mono- or multi-dentate ligands such as phosphines (trioctylphosphine, triphenylphosphine, t-butylphosphine etc.), phosphine oxides (trioctylphosphine oxide, triphenylphosphine oxide etc.), alkyl phosphonic acids, alkyl-amines (hexadecylamine, octylamine etc.), aryl-amines, pyridines, long chain fatty acids, thiophenes and the like.
The QD capping agent may also include or consist essentially of a coordinated ligand that processes additional functional groups that may be used as chemical linkage to other inorganic, organic or biological material, whereby the functional group is pointing away from the QD surface and is available to bond/react/interact with other available molecules, such as amines, alcohols, carboxylic acids, esters, acid chlorides, anhydrides, ethers, alkyl halides, amides, alkenes, alkanes, alkynes, allenes, amino acids, azides, groups etc. The capping agent may also include or consist essentially of a coordinated ligand that processes a functional group that is polymerisable and may be used to form a polymer layer around the particle.
The capping agent may also include or consist essentially of organic units that are directly bonded to the outermost inorganic layer such as via a disulfide (S—S) bond between the inorganic surface (e.g., ZnS) and a thiol capping molecule. These may also possess additional functional group(s), not bonded to the surface of the particle, which may be used to form a polymer around the particle, or for further reaction/interaction/chemical linkage.
QD-containing beads according to embodiments of the present invention may contain different sizes and/or types of QDs. For example, a QD-containing bead may contain one, two or more different types of QD. Depending upon the number of each QD present, the QD-containing bead will provide a particular overall colour upon excitation. These properties allow for colour tuning within the bead by the combination of different amounts of different colour QDs within separate beads. It is generally possible to produce QD-containing beads which emit light of any desirable colour, such as white light, by mixing suitable populations of red QDs, green QDs and Blue QDs within the same larger bead. This ‘colour mixing’ of the QDs may be achieved either within the QD-containing beads, i.e., each bead contains a number of differently sized and/or coloured QDs, and/or a mixture of differently coloured beads with all the QDs within a specific bead being the same size and/or colour, i.e., some beads containing all green QDs others containing all red QDs etc.
The versatility of embodiments of the present invention allows the use of wide varieties of polymers and carrier materials to form beads embedded with nanoparticles, particularly QDs. In principle, all types of polymers whether organic, or inorganic, water soluble or organic solvent soluble, biological or synthetic are suitable candidates. For example, the following simple linear chain polymers may be used: polyacrylate, polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde, polystyrene, polyethylene, polypropylene, poly ketone, polyether ether ketone, polyesters, polyamide, polyimide, polyacrylamide, polyolefines, polyacetylene, polyisoprene, polybutadiene, PVDF, PVC, EVA, PET, polyurethane, cellulose polymers (e.g., ethylcellulose, isopropylmethylcellulose phthalate, nitrocellulose), polyvinyl alcohol (PVA) and polyvinyl acetate (PVAc), polyvinylphenol. Further examples include crosslinked polymers and/or copolymers, triblock copolymers and UV- and thermal-curing epoxy. Clay materials such as bentonite, kaolin, fumed silica (e.g., cab-o-sil), fumed alumina, fumed zinc oxide, inorganic polymers may be used as the encapsulating medium alone or as additives to organic encapsulating polymers in order to improve the performance of the final QD-containing beads. Embodiments of the present invention may employ any of the polymers and materials indicated above alone or in combination with one or more of other suitable polymers and materials.
As well as encapsulating nanoparticles directly into the encapsulating medium, embodiments of the present invention also encompass the encapsulation of nanoparticles which are already fully or partly contained or encapsulated within an encapsulating medium. Thus, embodiments of present invention may include the encapsulation of pre-existing nanoparticle-containing beads into larger beads, preferably polymeric beads, formed of the encapsulating medium. The pre-existing nanoparticle-containing beads may be pre-prepared by any desirable process, including a process according to embodiments of the present invention.
The pre-prepared beads with the nanoparticles may be encapsulated into a bigger bead system by using the same process of aggregating both the pre-prepared beads (with the nanoparticles) and the system that makes the larger encapsulating beads, by applying a stimulus to the carrier solution (e.g., when the chemical environment is changed) to induce coaggregation of the pre-prepared beads and the encapsulating system.
In the case that the nanoparticles are QDs, a ‘core-shell’ QD-bead architecture may confer even greater protection against the degradation of the electronic properties of the encapsulated QDs compared to ‘simple’ QD-containing beads in which the QDs are encapsulated directly within a bead. The encapsulation of QD-containing beads into secondary ‘shelling’ beads produces QD-based materials which are particularly robust. QD leakage from the beads is minimized, making these materials prime candidates for a variety of applications in relatively harsh environments. For example, core-shell encapsulated QD-beads may mask any potential toxicity of the QDs in biological applications. Moreover, populations of differently coloured beads may be embedded in a single, robust, larger bead, thus enabling the development of colour-coded beads that may be used for multiplexed applications like anti-counterfeiting and various complicated tagging systems.
Another advantage of core-shell nanoparticle-containing beads is that it is possible to alleviate problems related to any incompatibility between the nanoparticle surface and the material, e.g., polymer, forming the outermost layer of the bead material which is required for a particular application. For example, it may be advantageous to embed nanoparticles capped with an organic surface-binding ligand initially into beads made of a hydrophobic polymer, and then design a core-shell bead architecture by encapsulating the beads formed initially into larger beads including a hydrophilic polymer to impart novel surface properties, for example, water solubility. Moreover, the same concept may be applied to core-shell beads in which the inner beads include a polymeric material which is of different or opposite charge to the polymeric material included in the outer bead(s).
Embodiments of the present invention preferably involve the initial step of dispersing a population of nanoparticles and an encapsulating medium, which is intended ultimately to encapsulate the nanoparticles, in a common solvent. The resulting solution system may be sufficiently stable when consisting essentially or solely of the nanoparticles, encapsulant and common solvent. In some applications it may be desirable to include one or more further species within the solution system, such as an additive to stabilise the dispersion of nanoparticles within the solution system. The method then preferably includes the step of destabilising the solution system by treating it with a suitable stimulus, such as a physical change, like an increase or decrease in temperature, and/or a chemical change, for example, the addition of a different solvent or mixture/blend of solvents, a change in pH, addition of a salting-out agent or a chaotropic agent.
In preferred embodiments a sample of nanoparticles (e.g., core/shell QDs, such as III-V/II-VI or, more specifically InP/ZnS) are dispersed in a suitable organic solvent (e.g., dichloromethane or toluene) together with an organic polymer which is intended to form the encapsulating bead material (e.g., polycarbonate, polybutadiene, polyisoprene, polyethylene, epoxy or poly(o-cresylglycidylether)-co-formaldehyde). The solvent is generally chosen so that it forms a stable dispersion with the particular encapsulating polymer as well as the nanoparticles. Dichloromethane is preferred for use with polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde and epoxy, while toluene is preferred for use with polybutadiene, polyisoprene and polyethylene.
Depending upon the nature of the encapsulating polymer being used it may be preferred to first heat the polymer up to or beyond its melting point, optionally in the presence of the organic solvent, before adding the nanoparticles to form an initial solution system. This is may be preferred, for example, when using polyethylene as the encapsulating polymer.
The nanoparticles may be combined with the encapsulating polymer and the solvent in the presence of a small amount (e.g., up to approximately 10 wt %, more preferably approximately 1 to 7 wt %, still more preferably approximately 5 wt % or approximately 1-2 wt %) of an additive, which is used to stabilise the nanoparticles within the resulting solution system. Suitable additives incorporate a nanoparticle surface-binding moiety and a moiety compatible with the solvent. Convenient additives include fatty acids, such as steric acid, which may bind to the surface of the nanoparticles via their terminal carboxyl groups, while their long hydrocarbon tails are directed outwardly, away from the nanoparticles into the organic solvent. The use of an additive, such as a fatty acid, is preferred when the encapsulating polymer is polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde, polybutadiene, polyisoprene or polyethylene. Still further preferred additives are based on saccharides and/or anti-oxidants, such as trehalose. It is preferred that such saccharide-based additives are silylated at some or all available positions within the sugar. Silylation is preferably achieved using trimethylsilyl groups. A particularly preferred additive, which is eminently useful for use with polycarbonate or poly(o-cresylglycidylether)-co-formaldehyde as the encapsulant, is trimethylsilyl-D-(+)-trehalose. When the encapsulating polymer is an epoxy it is preferred not to use a fatty acid-based additive.
The nanoparticle-containing solution system is then preferably contacted by a second solution system, which acts as a stimulus to destabilise the initial nanoparticle-containing solution system and induce spontaneous aggregation of the nanoparticles within discrete beads of the encapsulating polymer. The initial nanoparticle-containing solution system may be introduced into the second solution system or vice versa.
The second solution system may incorporate a surfactant-type species or a non-surfactant. Preferred second solution systems include aqueous solutions of methyl cellulose or polyethyleneglycol, silicone oil, or acetylnitrile.
The second solution system may include a polarity modifying agent which may be used to optimise the polarity of the second solution system. This provides a means by which the relative polarities of the first and second solution systems may be controlled, which may be used to influence the size and number of final nanoparticle-containing beads produced. While the inventors do not wish to be bound by any particular theory, it is believed that a lower difference in polarity between the first and second solvent systems generally produces a higher number of smaller nanoparticle-containing beads. Any appropriate amount of a polarity-modifying agent may be added to the second solution system. By way of example, the polarity-modifying agent may represent up to approximately 40 to 50% (V/V) of the second solution system. More preferably approximately 5 to 30% (V/V) or approximately 10 to 25% (V/V) of the second solution system may be the polarity-modifying agent. Most preferably the polarity-modifying agent represents approximately 20% (V/V) of the second solution system.
Following contacting of the two solution systems for a suitable period of time the original organic solvent may then be removed and the nanoparticle-containing polymer beads isolated and washed. Methyl cellulose is the preferred stimulus to induce spontaneous aggregation of the nanoparticle-beads and is particularly suitable for use with polycarbonate, polybutadiene and polyisoprene encapsulating polymers. If it is desired to produce smaller nanoparticle-containing beads in methyl celluclose then an amount of tetrahydrofuran may be added to the methyl cellulose to reduce the difference in polarity between the first and second solution systems, with the result of producing a greater number of smaller nanoparticle-containing beads. Other polarity modifiers may be used. Generally it is preferred that the polarity modifier is miscible in water and has a polarity index of approximately 4. Preferred examples include dioxane, acetonitrile, n-propanol, iso-propanol, methyl ethyl ketone and the like. Acetylnitrile may be used instead of methyl celluclose, particularly with polycarbonate as the encapsulating polymer. Polyethyleneglycol is particularly suitable for use with polyethylene as the encapsulating polymer. Silicone oil is the preferred stimulus for use when epoxy is the encapsulating polymer.
Once nanoparticle-encapsulant aggregation has generated the nanoparticle-containing beads it may be desirable to subject the beads to a further treatment step to improve their physical characteristics. For example, when an epoxy encapsulating polymer has been used, it is preferred that the initial nanoparticle-containing epoxy beads are subjected to a suitable heat-treatment process over a sufficient period of time to crosslink and ‘set’ the epoxy, thereby increasing the strength and robustness of the final epoxy beads.
The quantum efficiency of InP/ZnS nanoparticles encapsulated in a range of polymers employing the preferred embodiments of the present invention as explained above may be approximately 20 to 40%. More specifically, InP/ZnS QDs encapsulated within polycarbonate beads typically exhibited a PLQY of 35%; InP/ZnS QDs within polybutadiene beads typically exhibited a PLQY of 31%; InP/ZnS QDs within polyisoprene beads typically exhibited a PLQY of 23%; InP/ZnS QDs within polyethylene beads typically exhibited a PLQY of 24%; and InP/ZnS QDs within epoxy beads typically exhibited a PLQY of 20.3%.
Embodiments of the present invention relate to a method for producing encapsulated nanoparticles, particularly, but not exclusively, QD-containing polymeric beads, as well as the materials per se. The encapsulating material, also referred to herein as the “encapsulant,” is preferably an optically transparent or clear medium. QD-containing beads, preferably polymeric beads, produced by embodiments of the present invention have a number of advantages. The manufacturing process is relatively simple and avoids the use of harsh conditions, which therefore limits the potential damage that may occur to the QDs during encapsulation. As a result, the QDs embedded in the beads retain their original electronic properties to a greater extent than when encapsulated using prior-art techniques. Additional benefits include the fact that the QDs have increased protection compared to bare QDs from the surrounding chemical environment and photo-oxidation, as well as greater tolerance to processing conditions necessary for incorporation into solid-state structures. The simplicity and ease of embodiments of the present invention permit large-scale production of beads embedded with nanoparticles (QDs, colloidal metals, metal oxides etc.). Moreover, the ability to incorporate the nanoparticles into a variety of materials, including a wide range of polymers, confers better dispersibility and processability to the original QDs in the types of different mediums, such as resins, that are commonly used in applications like bio-labeling, light-emitting diodes (LEDs), solar cells, and lasers.
It will be appreciated that the scope of the present invention is not limited to the preferred embodiments described above and the examples described below and that said embodiments and examples may be modified without departing from the basic concept underlying each aspect of the present invention defined above.
EXAMPLES
Embodiments of the present invention are illustrated with reference to the following non-limiting examples.
Synthetic Methods
Preparation of CdSe Core Nanoparticles Capped with HDA
HDA (500 g) was placed in a three-neck round bottomed flask and dried and degassed by heating to 120° C. under a dynamic vacuum for >1 hour. The solution was then cooled to 60° C. To this was added 0.718 g of [HNEt3]4[Cd10Se4(SPh)16] (0.20 mmols). In total 42 mmols, 22.0 ml of TOPSe and 42 mmols, (19.5 ml, 2.15 M) of Me2Cd.TOP was used. Initially 4 mmol of TOPSe and 4 mmols of Me2Cd.TOP were added to the reaction at room temperature and the temperature increased to 110° C. and allowed to stir for 2 hours. The reaction was a deep yellow colour, the temperature was progressively increased at a rate of  ̃1° C./5 min with equimolar amounts of TOPSe and Me2Cd.TOP being added dropwise. The reaction was stopped when the photoluminescence (PL) emission maximum had reached about 600 nm by cooling to 60° C. followed by addition of 300 ml of dry ethanol or acetone.
This produced a precipitation of deep red particles, which were further isolated by filtration. The resulting CdSe particles were recrystallized by re-dissolving in toluene followed by filtering through Celite followed by re-precipitation from warm ethanol to remove any excess HDA, selenium or cadmium present. This produced 10.10 g of HAD-capped CdSe nanoparticles. Elemental analysis C=20.88%, H=3.58%, N=1.29%, Cd=46.43%. Max PL=585 nm, FWHM=35 nm. 38.98 mmols, 93% of Me2Cd consumed in forming the QDs.
Preparation of CdSe/ZnS Core/Shell Nanoparticles Capped with HDA
HDA (800 g) was placed in a three-neck round-bottom flask, dried and degassed by heating to 120° C. under a dynamic vacuum for >1 hour. The solution was then cooled to 60° C. To this was added 9.23 g of CdSe nanoparticles that have a PL maximum emission of 585 nm. The HDA was then heated to 220° C. To this was added by alternate dropwise addition a total of 20 ml of 0.5 M Me2Zn.TOP and 0.5 M, 20 ml of sulphur dissolved in octylamine. Three alternate additions of 3.5, 5.5 and 11.0 ml of each were made, whereby initially 3.5 ml of sulphur was added dropwise until the intensity of the PL maximum was near zero. Then 3.5 ml of Me2Zn.TOP was added dropwise until the intensity of the PL maximum had reached a maximum. This cycle was repeated with the PL maximum reaching a higher intensity with each cycle. On the last cycle, additional precursor was added once the PL maximum intensity been reached until it was between 5-10% below the maximum intensity, and the reaction was allowed to anneal at 150° C. for 1 hour. The reaction mixture was then allowed to cool to 60° C. whereupon 300 ml of dry “warm” ethanol was added which resulted in the precipitation of particles. The resulting CdSe/ZnS core/shell nanoparticles were dried before being re-dissolved in toluene and filtered through Celite, followed by re-precipitation from warm ethanol to remove any excess HDA. This produced 12.08 g of HDA capped CdSe/ZnS core/shell nanoparticles. Elemental analysis C=20.27%, H=3.37%, N=1.25%, Cd=40.11%, Zn=4.43%; Max PL 590 nm, FWHM 36 nm.
Preparation of InP Core Nanoparticles (Emission from 500-700 nm)
Di-butyl ester (100 ml) and Myristic acid (10.0627 g) were placed in a three-neck flask and degassed at 70° C. under vacuum for one hour. After this period, nitrogen was introduced and the temperature increased to 90° C. ZnS molecular cluster [Et3NH4][Zn10S4(SPh)16] (4.7076 g) was added and the mixture allowed to stir for 45 minutes. The temperature was then increased to 100° C. followed by the dropwise addition of In(MA)3 (1 M, 15 ml) followed by (TMS)3P (1 M, 15 ml). The reaction mixture was allowed to stir while increasing the temperature to 140° C. At 140° C., further dropwise additions of In(MA)3 (1 M, 35 ml) (left to stir for 5 minutes) and (TMS)3P (1 M, 35 ml) were made. The temperature was then slowly increased to 180° C. and further dropwise additions of In(MA)3 (1 M, 55 ml) followed by (TMS)3P (1 M, 40 ml) were made. By addition of the precursor in the manner above nanoparticles of InP may be grown with an emission maximum gradually increasing from 520 nm up to 700 nm, whereby the reaction may be stopped when the desired emission maximum has been obtained and left to stir at this temperature for half an hour. After this period, the temperature was decreased to 160° C. and the reaction mixture was left to anneal for up to 4 days (at a temperature approximately 20 to 40° C. below that of the reaction). A UV lamp was also used at this stage to aid in annealing.
The InP nanoparticles were isolated by the addition of dried degassed methanol (approx. 200 ml) via cannula techniques. The precipitate was allowed to settle and then methanol was removed via cannula with the aid of a filter stick. Dried degassed chloroform (approx. 10 ml) was added to wash the solid. The solid was left to dry under vacuum for 1 day. This produced 5.60 g of InP core nanoparticles. Elemental analysis: Max PL=630 nm, FWHM=70 nm.
Post-Preparative Treatments
The quantum yields of the InP nanoparticles prepared above were increased by washing with dilute HF acid. The nanoparticles were dissolved in anhydrous degassed chloroform (about 270 ml). A 50 ml portion was removed and placed in a plastic flask, flushed with nitrogen. Using a plastic syringe, the HF solution was made up by adding 3 ml of 60% w/w HF in water and adding to degassed THF (17 ml). The HF was added dropwise over 5 hours to the InP nanoparticles. After addition was complete the solution was left to stir overnight. Excess HF was removed by extracting through calcium chloride solution in water and drying the etched InP nanoparticles. The dried nanoparticles were re-dispersed in 50 ml chloroform for future use. PL max=567 nm, FWHM=60 nm. The quantum efficiencies of the InP core nanoparticles at this stage range from 25-90%
Preparation of InP/ZnS Core/Shell Nanoparticles
A 20 ml portion of the HF-etched InP core nanoparticles was dried down in a three-neck flask. 1.3 g myristic acid and 20 ml di-n-butyl sebacate ester was added and degassed for 30 minutes. The solution was heated to 200° C. then 1.2 g anhydrous zinc acetate was added and 2 ml 1 M (TMS)2S added dropwise (at a rate of 7.93 ml/hr). After the addition was complete the solution was left to stir. The solution was kept at 200° C. for 1 hr then cooled to room temperature. The nanoparticles were isolated by adding 40 ml of anhydrous degassed methanol and centrifuged. The supernatant liquid was disposed of and 30 ml of anhydrous degassed hexane was added to the remaining solid. The solution was allowed to settle for 5 hours and then re-centrifuged. The supernatant liquid was collected and the remaining solid was discarded. PL emission peak Max.=535 nm, FWHM=65 nm. The quantum efficiencies of the InP/ZnS core/shell nanoparticles at this stage ranged from 35-90%.
Example 1
Preparation of InP/ZnS Core/Shell Nanoparticles Encapsulated in Polycarbonate
100 ml of a 1% w/v solution of methyl cellulose was prepared and placed in a single-necked round bottom flask, under nitrogen, equipped with a magnetic stirrer and stirring at 1500 rpm. A solution containing 30 mg of InP/ZnS core/shell nanoparticles in 5 ml of dichloromethane and 500 mg of polycarbonate polymer with 1% stearic acid (incubated for 24 hours at room temperature) was injected quickly as a single shot directly into the methyl cellulose solution. The dichloromethane was removed by using a rotary evaporator set at a vacuum of 800 mbar, rotor speed 3, and a water bath temperature of 40° C. for 2-3 hours. The particles were washed three times by centrifugation with deionized water, followed by a further three times with ethanol, and then isolated as a pellet. The final pellet was dried under vacuum over night. The quantum efficiency of the InP/ZnS nanoparticles encapsulated in the polycarbonate polymer was PLQY=35%.
Example 2
Preparation of InP/ZnS Core/Shell Nanoparticles Encapsulated in Polybutadiene
100 ml of a 1% w/v solution of methyl cellulose was prepared and placed in a single-necked round bottom flask, under nitrogen, equipped with a magnetic stirrer and stirring at 1500 rpm. A solution containing 30 mg of InP/ZnS core/shell nanoparticles in 5 ml of toluene and 500 mg of polybutadiene polymer with 1 stearic acid (incubated for 1 hour at room temperature) was injected quickly as a single shot directly into the methyl cellulose solution. The toluene was removed by using a rotary evaporator set at a vacuum of 800 mbar, rotor speed 3, and a water bath temperature of 40° C. for 1 hour. The nanoparticles were washed six times with deionized water and isolated as a single piece of polymer. The quantum efficiency of the InP/ZnS nanoparticles encapsulated in polybutadiene was PLQY=31%.
Example 3
Preparation of InP/ZnS Core/Shell Nanoparticles Encapsulated in Polyisoprene
100 ml of a 1% w/v solution of methyl cellulose was placed in a single-necked round bottom flask, under nitrogen, equipped with a magnetic stirrer and stirring at 1500 rpm. A solution containing 30 mg of InP/ZnS core/shell nanoparticles in 5 ml of toluene and 500 mg of polyisoprene polymer with 1 stearic acid (incubated for 1 hour at room temperature) was injected quickly as a single shot directly into the methyl cellulose solution. The toluene was removed by using a rotary evaporator set at a vacuum of 800 mbar, rotor speed 3, and a water bath temperature of 40° C. for 1 hour. The particles were washed six times with deionized water. The quantum efficiency of the InP/ZnS nanoparticles encapsulated in polyisoprene was PLQY=23%.
Example 4
Preparation of InP/ZnS Core/Shell Nanoparticles Encapsulated in Polyethylene
A solution of 2.5 ml of polyethylene in 10 ml of toluene containing 1% of stearic acid was placed in a three-necked 100 ml round bottom flask, under nitrogen, equipped with a magnetic stirrer and stirring at 1500 rpm. The mixture was heated to melting at 120° C. under reflux. Once the solution had melted, 130 mg of InP/ZnS core/shell nanoparticles was added and the nanoparticle/polyethylene solution was allowed to stir at 120° C. under reflux for 1 hour at 1500 rpm. After this time 50 ml of polyethyleneglycol-200 (PEG-200) was injected directly down the reflux condenser. The nanoparticles were washed three times with ethanol, centrifuged and the supernatant was removed. The particles were dried under vacuum in a sealed glass tube for 24 hours. The quantum efficiency of the InP/ZnS nanoparticles encapsulated in polyethylene was PLQY=24%.
Example 5
Preparation of Organic Acid-Capped InP/ZnS Core/Shell Nanoparticles Encapsulated in Thermosetting Epoxy
A 100 ml of degassed silicone oil was placed in a single-necked round bottom flask, under nitrogen, equipped with a magnetic stirrer and stirring at 1500 rpm. A solution containing 30 mg of InP/ZnS core/shell nanoparticles in 5.0 ml of dichloromethane and 1 ml of epoxy (incubated for 1 hour at room temperature) was injected quickly as a single shot directly into the silicone oil solution. After nanoparticle-containing polymer particles had formed, the solution was stirred at room temperature under nitrogen for three days to crosslink the epoxy. A rotary evaporator, set at a vacuum of 500 mbar, rotor speed 3, and a water bath temperature of 500° C. for 1 hour, was used to remove the dichloromethane and to crosslink the epoxy. The solution was transferred to a 50 ml Vulcan tube and washed six times with 20 ml of hexane. The particles were dried under vacuum in a sealed glass tube for 2 hours. The quantum efficiency of the InP/ZnS nanoparticles encapsulated in thermosetting epoxy was PLQY=20.3%.
Example 6
Preparation of QDs Encapsulated in Fumed Silica
Two grams of fumed silica (e.g., Cabosil®, Aerosil®) were prepared in a flask and degassed overnight. Then 500 mg of inorganic QDs was injected and mixed by intensive stirring. The mixture was continuously stirred at 500 rpm under an N2 atmosphere at an elevated temperature of 70 to 150° C. overnight, the temperature change to 70 to 150° C. acting as the stimulus to induce simultaneous aggregation of the nanoparticles and the silica-based encapsulating medium. The solvent was then evaporated to obtain the Cabosil-encapsulated QDs in the form of a dried power.
Example 7
Trimethylsilyl-D-(+)-Trehalose as an Additive in Polycarbonate (PC) Beads Containing Quantum Dots (QDs) in Methyl Cellulose
100 ml of a 1% w/v solution of methyl cellulose was prepared and placed in a single-necked round bottom flask, under nitrogen, equipped with a magnetic stirrer. The solution was degassed using nitrogen. 30 mg of inorganic QDs were taken and the toluene evaporated off under vacuum. The QDs were re-suspended in 4.5 ml dichloromethane (DCM) plus 0.5 ml of trimethylsilyl-D-(+)-trehalose (50 mg 5% w/w polymer). 1.0 g of PC in 5.0 ml DCM was added to the QD solution and stirred until the PC dissolved. The QD/PC solution was allowed to stand at room temperature with gentle stirring for 1 h. The QD/PC solution was then added to the 100 ml of the methyl cellulose solution with stirring at 1500 rpm. The DCM was vacuumed off and the PC-encapsulated QD beads spun out of solution at 500 rpm in a centrifuge. The supernatant was removed and the PC-encapsulated QD beads were washed three times with water and then three times with ethanol. The final PC-encapsulated QD bead residue was dried under vacuum to obtain PC-encapsulated QD beads with an external quantum yield of 36%, as compared to 24% for the same type of material but produced without the addition of trimethylsilyl-D-(+)-trehalose.
As well as improving the final quantum yield of the PC-encapsulated QD beads, trimethylsilyl-D-(+)-trehalose also improved the stability of the QDs in the PC beads by >20 times as compared to PC beads without trimethylsilyl-D-(+)-trehalose added. This is clear from a stability study in when the beads were used as a phosphor material in LED fabrication. The results are shown in FIG. 6.
Example 8
Controlling Bead Size by Adjusting Solvent Polarity—I
Formation of QD Beads Using PC/Trehalose in 1% Methyl Cellulose with 20% THF
The QD-containing particles produced above in Example 7 had a diameter of approximately 50 to 100 microns. Investigations were then conducted to determine how to change the diameter of the particles formed. The effect of changing the surface tension between the hydrophobic and hydrophilic phases of the solvent system in which the encapsulated QDs are produced was investigated by the addition of further solvents to the methyl cellulose to optimize its polarity.
PC-encapsulated QD beads were produced using the same procedure as set out above in Example 7 except that 20% of THF (V/V) was added to the 1% methyl cellulose. This produced much smaller spherical QD-containing particles of 5-10 micron diameter (see FIG. 7).
Example 9
Controlling Bead Size by Adjusting Solvent Polarity—II
Formation of QD Beads Using Poly(o-Cresylglycidylether)-co-Formaldehyde/Trehalose in 1% Methyl Cellulose with 20% THF
Encapsulated QD beads were produced using the same procedure as set out above in Example 8 except that the polycarbonate was replaced with poly[o-cresylglycidylether)-co-formaldehyde. This produced small spherical QD-containing particles (see FIG. 8).
It will be seen that the techniques described herein provide a basis for improved production of nanoparticle-based materials. The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms of and expressions of excluding any equivalents of the features shown and described or portions thereof. Instead, it is recognized that various modifications are possible within the scope of the invention claimed.

## Claims

1. A method for producing encapsulated nanoparticles, the method comprising:
dispersing a plurality of nanoparticles and an encapsulating medium in a first solution system; and
applying a stimulus to said first solution system to induce simultaneous aggregation of the nanoparticles and the encapsulating medium, wherein
said stimulus comprises a chemical change to the first solution system resulting in simultaneous aggregation of the nanoparticles and the encapsulating medium.

2. A method according to claim 1, wherein said stimulus destabilises the first solution system so as to induce said simultaneous aggregation.

3. A method according to claim 1, wherein said stimulus comprises a physical change to the first solution system resulting in simultaneous aggregation of the nanoparticles and the encapsulating medium.

4. A method according to claim 1, wherein said chemical change comprises a change selected from the group consisting of: changing the pH of the first solution system, addition of a salting-out agent to the first solution system, and addition of a chaotropic agent.

5. A method according to claim 1, wherein said chemical change comprises contacting the first solution system with a second solution system having at least one of a polarity or a chemical composition different from that of the first solution system.

6. A method according to claim 5, wherein the first solution system is introduced into the second solution system.

7. A method according to claim 5, wherein the second solution system is introduced into the first solution system.

8. A method according to claim 5, wherein the second solution system comprises a surfactant-type species.

9. A method according to claim 5, wherein the second solution system comprises a non-surfactant.

10. A method according to claim 5, wherein the second solution is selected from the group consisting of: an aqueous solution of methyl cellulose, an aqueous solution of polyethyleneglycol, silicone oil, and acetylnitrile.

11. A method according to claim 5, wherein the second solution system comprises a polarity-modifying agent.

12. A method according to claim 11, wherein the polarity-modifying agent decreases a difference in polarity between the first and second solution systems.

13. A method according to claim 11, wherein the polarity-modifying agent increases a difference in polarity between the first and second solution systems.

14. A method according to claim 11, wherein the polarity-modifying agent is miscible in water and has a polarity index of approximately 4.

15. A method according to claim 11, wherein the polarity modifying agent is selected from the group consisting of: dioxane, acetonitrile, n-propanol, isopropanol, and methyl ethyl ketone.

16. A method according to claim 5, further comprising, after contacting the first and second solution systems for a sufficient time to induce simultaneous aggregation of the nanoparticles and the encapsulating medium, removing the common solvent and isolating the encapsulated nanoparticles.

17. A method according to claim 1, wherein the nanoparticles are combined with the encapsulating medium and the common solvent in the presence of an additive to stabilise the nanoparticles within the first solvent.

18. A method according to claim 17, wherein said additive is selected from the group consisting of: a fatty acid, a saccharide, and an antioxidant.

19. A method according to claim 1, wherein said common solvent is an organic solvent.

20. A method according to claim 1, wherein after aggregation of the nanoparticles and the encapsulating medium the aggregate is subjected to a further treatment step to improve the physical properties of the aggregate.

21. A method according to claim 20, wherein the encapsulating medium is an epoxy and said further treatment step comprises crosslinking of the epoxy encapsulating medium.

22. A method according to claim 1, wherein the encapsulating medium is a polymeric encapsulating medium selected from the group consisting of: an organic polymer, an inorganic polymer, a water-soluble polymer, an organic-solvent-soluble polymer, a biological polymer, and a synthetic polymer.

23. A method according to claim 1, wherein the encapsulating medium is a polymeric encapsulating medium selected from the group consisting of: polyacrylate, polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde, polystyrene, polyethylene, polypropylene, poly ketone, polyether ether ketone, polyester, polyamide, polyimide, polyacrylamide, polyolefine, polyacetylene, polyisoprene, polybutadiene, poly(vinylidene fluoride), poly(vinyl chloride), ethylene vinyl acetate, polyethylenetelephthalate, polyurethane, and cellulose polymers.

24. A method according to claim 1, wherein the encapsulating medium is a polymeric encapsulating medium selected from the group consisting of: a crosslinked or crosslinkable polymer, a crosslinked or crosslinkable copolymer, a triblock copolymer, a UV-curable epoxy polymer, and a thermally curable epoxy polymer.

25. A method according to claim 1, wherein the encapsulating medium is selected from the group consisting of: bentonite, kaolin, fumed silica, fumed alumina, and fumed zinc oxide.

26. A method according to claim 1, wherein the encapsulating medium is a polymeric encapsulating medium selected from the group consisting of: polycarbonate, poly(o-cresylglycidylether)-co-formaldehyde, polybutadiene, polyisoprene, polyethylene, and epoxy.

27. A method according to claim 1, wherein the encapsulating medium is optically transparent.

28. A method according to claim 1, wherein the nanoparticles are semiconductor nanoparticles.

29. Encapsulated nanoparticles produced using a method according to claim 1.