EP1909955A2

EP1909955A2 - Hollow nanocapsules

Info

Publication number: EP1909955A2
Application number: EP06775744A
Authority: EP
Inventors: Joachim Koetz; Volker Abetz; Stefanie Lutter
Original assignee: Universitaet Postdam
Current assignee: Universitaet Postdam
Priority date: 2005-07-22
Filing date: 2006-07-21
Publication date: 2008-04-16
Also published as: WO2007009455A2; WO2007009455A3; DE102005035374A1

Abstract

Disclosed are hollow nanocapsules which are obtained by mixing microemulsions and modifying the same by means of block copolymers. Also disclosed are a method for producing hollow nanocapsules as well as the use thereof.

Description

Nano hollow capsules

The invention relates to nano hollow capsules, a process for their preparation and uses of the nano hollow capsules.

The object of the present invention is to produce the smallest possible cavities in which substrates are stored and which can serve as reactor space for the nanoparticle formation.

Nanoparticles have special properties. The special properties of nanoparticles are achieved, inter alia, by the fact that the surface is very large compared to the volume. Due to the large surface, e.g. very good catalytic and optoelectronic properties can be achieved. Another property of nanoparticles is that they can be easily incorporated into other materials or composite materials such as paints, emulsions, films and membranes.

The object of the present invention is achieved by nano-hollow capsules obtainable by mixing microemulsions modified with block copolymers.

After mixing the microemulsions, a work-up step follows.

Nanohohlkapseln are able to store substances. Thus, it is possible to use nano hollow capsules e.g. to use for wastewater treatment. In the wastewater, the nano-hollow capsules store metals in their interior and thus remove them from the wastewater.

The nano hollow capsules preferably have a diameter of 5 nm to 1000 nm. This has the advantage that the Na are smaller than microcapsules, as they are used in various fields of medicine, pharmacy, in the food industry and many other areas. As a result, they are useful for many new applications where microcapsules are not suitable because they are too large.

The microemulsion is preferably water, long chain alcohols (e.g., heptanol) and / or an oil component (e.g., toluene), and surfactants (e.g., sodium dodecyl sulfate (SDS)).

The microemulsion is preferably modified with polymers.

The polymers are preferably water-soluble polyelectrolytes and / or oil-soluble polymers.

In a preferred embodiment of the invention, the polyelectrolytes are selected from water-soluble ionic polymers. The polyelectrolytes contribute to the stabilization of the nano-hollow capsules or control the formation of nanoparticles in the interior of the hollow capsules.

The polyelectrolytes are preferably selected from anionic polyacids, cationic polybases or neutral polyamolytes or polysalts. Polyelectrolytes are water-soluble ionic polymers which are anionically formed from polyacids (for example polycarboxylic acids), cationically from polybases (for example polyvinylamines) or which are neutral (polyampholytes or polysalts).

The block copolymers preferably consist of two or more blocks. Good results are achieved with the admixture of block copolymers consisting of three blocks. A part of the block copolymer is polymerizable.

The blocks of the block copolymers preferably have different properties, the properties being selected from the group of hydrophilic, polymerizable and / or hydrophobic properties.

The different blocks are preferably characterized by being hydrophilic, polymerizable and / or hydrophobic.

For example, the triblock copolymer SBEO is suitable for the preparation of the nano-hollow capsules. This is a copolymer which is composed of a styrene, a butadiene and an ethylene oxide block and is referred to as S ₄₃ B ₂ 1EO ₃₆ . It has an average molecular weight of about 110,000 g / mol. Due to its structure, the copolymer should be arranged in a W / O microemulsion so that the hydrophobic block in the oil phase and the hydrophilic ethylene oxide block penetrate into the aqueous phase. The Butadienblock then arranges in the region of the interface between water droplets and oil phase. Such a structure opens up the possibility of initializing additional crosslinking via the double bonds of the butadiene block. This leads to a spatial limitation of the water droplet and the particle formation occurring therein.

Preferably, the nano-hollow capsules are cross-linked by crosslinking of the polymerizable blocks of the block copolymers. The block copolymers penetrate with their hydrophilic or hydrophobic block, the microemulsion droplets. The fact that the block copolymers additionally contain a polymerizable block, the formation of a covalently sealable polymer layer around the droplet or the nanoparticles formed therein allows.

In a preferred embodiment of the invention, the nano-hollow capsules are prefilled. By pre-filling the nano-hollow capsules, nanoparticles can be formed when mixing two microemulsions, which can be used in a variety of ways.

It is thus possible to pre-fill the nano-hollow capsule with a wide variety of substances and thus obtain nanoparticles which have a great variety of properties.

The nano-hollow capsules are preferably prefilled with metal salts, metal halides, reducing agents, pharmacologically active substances, magnetically and / or optically active reagents or polymers. As magnetic substances, for example, magnetite (Fe ₃ O ₄ ) or ferrites such as CoFe ₂ O ₄ can be used.

In order for this pre-filling to be achieved, the microemulsion preferably contains metal salts and / or reducing agents, which then serve as precursors for the construction of the pre-filled nano hollow capsule.

Furthermore, the object of the present invention is achieved by a process for the preparation of nano hollow capsules in which at least two microemulsions are mixed together, which is modified with block copolymers and polymers and then worked up the resulting nano hollow capsules.

The stability of the shell and the size of the particles can be controlled by the concentrations of the individual reaction components and the reaction conditions. The resulting particles with polymer surface can be freed from the solvent mixture and re-dispersed in other solvents - a suitable solvent is water.

The covalent encapsulation of the nano-hollow capsules offers the advantage that changes of a chemical or physical nature are minimized in all subsequent reaction steps.

In addition, the use of the block copolymers makes it possible to modify the surface of the nanoparticles.

Preferably, inverse microemulsions of water, an oil component, long-chain alcohols and / or surfactants are added. As the oil component, e.g. Xylene, toluene, isooctane, heptanol, cyclohexane, hexadecane and / or n-octane.

The preferred polymers include water-soluble polyelectrolytes for W / O microemulsions and oil-soluble polymers for O / W microemulsions. In this case, if water is the outer and oil is the inner phase, there is an O / W emulsion whose basic character is characterized by water. If oil is the outer and water is the inner phase, there is a W / O emulsion, whereby the basic character of the oil is determined here.

More preferably, water-soluble ionic polymers are added as polyelectrolytes. By adding polyelectrolytes, the stability of the nano-hollow capsules can be controlled.

The polymers used are preferably anionic from polyacids (eg polycarboxylic acids), cationic from polybases (eg polyvinylamines) or neutral polyampholytes or polysalts.

The polymer used is preferably oil-soluble polymers and / or oil-in-water microemulsions.

Furthermore, it is preferable to add electron-acceptor and electron-donor polymers as oil-in-water microemulsions.

In a preferred embodiment of the invention, block polymers of at least two blocks are added, the blocks having different properties and the properties of the blocks selected from the group of hydrophilic, hydrophobic or polymerizable properties.

Preference is given to adding different blocks, which are characterized in that they are hydrophilic, hydrophobic and / or polymerizable.

By selecting the block copolymers, the size of the nano-hollow capsules can be controlled. The larger the block copolymers, the larger the nano hollow capsules.

The polymerizable blocks of the block copolymers are preferably crosslinked so that the nano hollow capsules are polymer-coated. The polymerization can be effected via the addition of a radical initiator, e.g. of azoisobutyronitrile (AIBN) thermally or else initiated by radiation.

In a preferred embodiment of the invention, the nano-hollow capsules are pre-filled with pharmacologically active substances, magnetically or optically active substances. It is possible to pre-fill the nano-hollow capsules during their formation. For this purpose, the desired substances are added to the microemulsion, which then serve as precursors for the formation of the nano-hollow capsules.

Preferably, the microemulsion is mixed with metal salts, metal halides and / or reducing agents.

In a preferred embodiment of the invention, the nanohull capsules are filled in a further step.

Preferably, the nano hollow capsules are filled with metals, metal halides, metal oxides, metal salts, pharmacologically active substances, magnetic, optical or radioactive substances, color pigments or contrast agents. The pre-filling of the nano-hollow capsules yields nanoparticles with a wide variety of properties. Magnetic nanoparticles can be produced, for example, by prefilling with magnetite Fe ₃ O ₄ or ferrite, such as Co-Fe ₂ O ₄ . Optoelectronic interesting

Nanoparticles can be pre-filled with CdS, CdSe and / or ZnS, for example. Catalytically interesting nanoparticles are, for example, nano hollow capsules prefilled with gold (Au), platinum (Pt) and / or palladium (Pd). In addition, it is possible to produce core-shell particles.

Furthermore, the object of the present invention is achieved by using nano-hollow capsules, for the transport of pharmacologically active substances into the human or animal body. In addition to the transport of pharmacologically active substances, the transport of other substances (eg metals, metal halides, metal oxides, metal salts, magnetic, optical and / or radioactive substances, X-ray contrast media, eg BaSO ₄ ) in the human or animal body using the nano-hollow capsules possible.

Furthermore, the object of the present invention by the use of nano hollow capsules for the preparation of medicaments for the transport of pharmacologically active substances in the human and animal body is achieved.

The interior of the nano-hollow capsules makes it possible to absorb pharmacologically active substances and to introduce them in this way in the human or animal body. As a result, a delayed release of active ingredients in the body can be achieved.

It is also possible to use the nano-hollow capsules to protect against an environmental milieu, as taste / odor masking, for long-term stabilization, controlled release, dosing and mixing, prevention of contamination and / or to reduce allergenic effects.

Furthermore, the object of the present invention is achieved by using pre-filled nano hollow capsules as nanoparticles. It is not only possible that

To fill nano-hollow capsules after their production, but also perform a pre-filling of the nano-hollow capsules during production. In this way, nanoparticles are obtained which have a polymer coating.

Furthermore, the object of the present invention is achieved by using pre-filled nano hollow capsules for coating surfaces. Another solution of the present invention is the use of pre-filled nano hollow capsules for incorporation in polymer membranes.

Possible fields of application of the nano hollow capsules are the

Textile industry, dyeing and lacquer industry (flakes, pigments, antifoulings), construction industry (heat storage, pest control), printing and paper industry, electroplating (installation of eg corrosion protection and shing mittein) or in the plastics industry.

In the following the invention will be described in more detail with reference to figures and examples. In detail shows

FIG. 1a shows a nano hollow capsule consisting of surfactant molecules and diblock copolymers,

FIG. 1 b shows a nano hollow capsule consisting of surfactant molecules and triblock copolymers,

FIG. 1c shows the structure of a triblock copolymer,

FIG. 2 shows the particle size distribution according to Example 1,

FIG. 3 shows the particle size distribution according to Example 2,

FIG. 3 shows the particle size distribution according to Example 3,

FIG. 4 shows the particle size distribution according to Example 4,

FIG. 5 shows the particle size distribution according to Example 5,

FIG. 6 shows the particle size distribution according to Example 6,

FIG. 7 shows the particle size distribution according to Example 7,

FIG. 8 shows the particle size distribution according to Example 8,

FIG. 9 the particle size distribution according to Example 9,

FIG. 10 shows the particle size distribution after the first

Mixture according to Example 10 and

11 shows the Teilchengrδßenverteilung after the second

Mixture according to Example 10. FIG. 1a shows a section through a nano-hollow capsule 1 consisting of surfactant molecules 2 and diblock copolymers. The Nanonholkapsel 1 is formed by a scaffold of surfactant molecules 2. Between the surfactant molecules 2 block copolymers 3 are incorporated into the scaffold. The block copolymers 3 consist of a hydrophilic part 3a and a hydrophobic part 3b, wherein the block copolymers 3 are arranged so that they reach into the interior 4 of the nano hollow capsules 1 with the hydrophilic part 3a and with the outer, hydrophobic part 3b the outer layer of the nano hollow capsules 1 form.

FIG. 1b shows an analogous scheme for a triblock copolymer 5, the middle block 3c being polymerizable.

Figure Ic shows an example of the structure of a triblock polymer 5 consisting of a hydrophilic part 3a, a hydrophobic part 3b and a polymerizable part 3c.

FIGS. 2 to 6 show diagrams of the dynamic light scattering analysis results on the Nano Zetasizer (Maillers Instruments) for Examples 1 to 4, 6 and 7. In the diagrams, the size of the particles in nm is plotted in relation to the intensity in percent.

FIG. 2 shows the particle size distribution measured in the production of nano-hollow capsules according to Example 1. The mean particle diameter (Z-average) is 225 nm.

FIG. 3 shows the particle size distribution according to Example 2. The mean particle diameter (Z-average) is 119 nm here. FIG. 4 shows the particle size distribution according to the example

3. The mean particle diameter (Z-average) is 224 ntn here.

FIG. 5 shows the particle size distribution according to the example

4. The mean particle diameter (Z-average) is 213 nm here.

FIG. 6 shows the particle size distribution according to Example 6. The mean particle diameter (Z-average) here is 214 nm.

FIG. 7 shows the particle size distribution according to example

7. The mean particle diameter (Z-average) is 689 nm here.

FIG. 8 shows the particle size distribution according to the example

8. The mean particle diameter (Z-average) is 15 nm here.

FIG. 9 shows the particle size distribution according to example

9. The mean particle diameter (Z-average) is 9 nm here.

Figures 10 and 11 show the particle size distribution of the mixtures described in Example 10. The mean particle diameter (Z-average) in the first mixture (FIG. 10) is 175 nm and that of the second mixture (FIG. 11) is 200 nm.

Example 1 (Production and Characterization of Nano-Capsules):

For the preparation of the nano hollow capsules were triblock copolymers, consisting of a styrene (S), a butadiene

(B) and an ethylene oxide block in xylene / pentanol (1: 1), Sodium dodecyl sulfate (SDS) and water mixed. The resulting slightly opaque solutions were then characterized by light scattering.

Composition of the mixture: ^■ => 1 g of water; 1 g SDS

7.92 g of xylene, pentanol (1: 1) 0.08 g of block copolymer S _I4 B ₄₅ EO ₄₀

Analysis of dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter of 225 nm (see FIG. 2).

Example 2 (Production and Characterization of Nano-Capsules):

To prepare the nano-hollow capsules were triblock copolymers consisting of a styrene (S), a butadiene (B) and an ethylene oxide block in xylene / pentanol (1: 1),

Sodium dodecyl sulfate (SDS) and water mixed. The resulting slightly opaque solutions were then characterized by light scattering.

Composition of the mixture: ^■ => 1 g of water; 1 g SDS

7.92 g of xylene, pentanol (1: 1) 0.08 g of block copolymer Si ₈ B ₃₆ EO ₄₆

Analysis of dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter of 119 nm (see FIG. 3). Example 3 (Barium sulfate filled nano hollow capsules): Two nano hollow capsule mixtures were each prefilled with a 2 mmol BaCl ₂ solution or with a 2 mmol Na ₂ SO ₄ solution. After addition of adequate amounts of both mixtures (2 ml each), scattered-light photometric investigations were carried out on the barium sulfate-containing nano-hollow capsules:

Composition of the mixture 1: ^■ => 1 g (2 mmol) BaCl ₂ solution; 1 g SDS

7.92 g of xylene, pentanol (1: 1) 0.08 g of block copolymer S ₁₄ B ₄₆ EO ₄₀

Composition of the mixture 2: ■ => 1 g (2 mmol) of Na ₂ SO ₄ solution; 1 g SDS

7.92 g of xylene, pentanol (1: 1) 0.08 g of block copolymer Si ₄ B ₄₆ EO ₄₀

The analysis of the dynamic light scattering at the Nano Zetasi-

® zer (Malvern Instruments) gave an average particle diameter of 224 nm (see FIG. 4).

Example 4 (Crosslinking of barium sulfate filled nano hollow capsules):

In the presence of a crosslinker (azoisobutyronitrile (AIBN)), in analogy to example 3, two nanohydrocarbon mixtures were each pre-filled with BaCl ₂ or Na ₂ SO ₄ . After co-administration of appropriate amounts of both mixtures (2 ml each), and completion of nanoparticle formation the mixture was heated to 60 ⁰ C, the radical crosslinking of the butadiene blocks of the block copolymer to tiieren ini. Following crosslinking, scattered-light photometric investigations were again carried out: Composition of the AIBN-containing mixture 1: <=> 1 g (2 mmol) BaCl ₂ solution;

1 g SDS 7.92 g xylene, pentanol (1: 1) (0.03% AIBN) 0.08 g block copolymer Si ₄ B ₄₆ EO ₄₀

Composition of the AIBN-containing mixture 2: ^■ => 1 g (2 mmol) of Na ₂ SO ₄ solution; I g SDS

7.92 g of xylene, pentanol (1: 1) (0.03% AIBN)

0.08 g of block copolymer S ₁₄ B ₄₆ EO ₄₀

Analysis of the dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter of 213 nm (see FIG. 5).

Example 5 (Gold filled nano capsules): Two nano capsule mixtures were each mixed with a

2 mmol HAuCl ₄ solution or prefilled with a 40 mmol NaBH ₄ solution. After combining both mixtures in a ratio of 1: 2, scattered light photometric investigations were carried out on the gold-containing nano-hollow capsules:

Composition of the mixture 1: <=> 1 g (2 mmol) HAuCl ₄ solution;

1 g SDS

7.92 g of xylene, pentanol (1: 1) 0.08 g of block copolymer S ₄₃ B _2I EO ₃₆

Composition of Mixture 2: ^■ => 1 g (40 mmol) of NaBH ₄ solution;

1 g SDS 7.92 g xylene, pentanol (1: 1)

0.08 g of block copolymer S ₄₃ B ₂₁ EO ₃₆ The analysis of the dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter of 336 nm.

Example 6 (Crosslinking of Gold-filled Nanohohl Capsules):

In the presence of a crosslinker (azoisobutyronitrile (AIBN)), two nanohohl capsule mixtures were prefilled in each case with a 2 mmol HAuCl ₄ solution or with a 40 mmol NaBH ₄ solution in analogy to Example 5. After combining both mixtures in a 1: 2 ratio and nanoparticle formation, the mixture was heated to 60 ^° C. to initiate radical crosslinking of the butadiene blocks of the block copolymer. Following crosslinking, scattered-light photometric investigations were again carried out:

Composition of the AIBN-containing mixture 1: <=> 1 g (2 mmol) of HAuCl ₄ solution; 1 g SDS

7.92 g of xylene, pentanol (1: 1) (0.03% AIBN) 0.08 g of block copolymer S ₄₃ B _2I EO ₃₆

Composition of AIBN-containing mixture 2: <= 1 g (40 mmol) of NaBH ₄ solution; 1 g SDS

7.92 g of xylene, pentanol (1: 1) (0.03% AIBN) 0.08 g of block copolymer S ₄₃ B ₂ IEO ₃₆

Analysis of the dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter of 214 nm (see FIG. 6). Example 7 (Redispersion of Gold-filled Nano-Capsules):

The resulting mixture of Example 6 was dried in a vacuum oven at a temperature of 35 ⁰ C for 2 days. The residue was redispersed in toluene and then analyzed by scattered light photometry.

Analysis of the dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter (Z-average) of 689 nm (see FIG. 7).

Example 8 (Preparation and Characterization of Nano-Capsules):

Triblock copolymers consisting of a styrene (s), a butadiene (B) and an ethylene oxide block (EO) in xylene / pentanol (1: 1), sodium dodecyl sulfate (SDS) and water were blended to form the nano hollow capsules. The resulting optically clear solutions were subsequently characterized by light scattering.

Composition of the mixture: ^■ => 1 g of water I g SDS

7.6 g of xylene, pentanol (1: 1)

0.4 g of block copolymer Si ₈ B ₃₆ EO ₄₆

The analysis of the dynamic light scattering zer on Nano Zetasi- (Malvern Instruments ^®) resulted in a mean particle keldurchmesser of 15 nm (see Figure 8).

Example 9 (Preparation and Characterization of Crosslinked Nanoclave Capsules): In the Presence of a Crosslinker (Azoisobutyronitrile

(AIBN)), in analogy to Example 8, a nanohydrocarbon kapsei - Mixture made. The mixture was then heated to 80 ° C to initiate radical crosslinking of the butadiene blocks of the block copolymer. Subsequent to crosslinking, scattered photometric studies were again performed.

Composition of the AIBN-containing mixture: ^■ => 1 g of water

1 g SDS 7.6 g xylene, pentanol (1: 1) (0.1% AIBN)

0.4 g of block copolymer Si ₈ B ₃₆ EO ₄₆

Analysis of dynamic light scattering on the nano-cetaser (Malvern Instruments) revealed a mean particle diameter of 9 nm (see FIG. 9).

Example 10 (preparation and characterization of polyelectrolyte-modified nano hollow capsules): In analogy to Example 1, nano hollow capsule

Mixtures prepared in which the proportion of water was replaced by a solution of the cationic polyelectrolyte poly (diallyl dimethyl ammonium chloride) (PDADMAC) in water. The resulting slightly opaque solutions were then characterized by light scattering.

Composition of the mixture:

^■ => 1% aqueous PDADMAC solution I g SDS

The analysis of the dynamic light scattering on the nanozetazizerrer ((MMaallvveerrnn IInnssttrruummennttss)) gives a smaller particle diameter of 175 nm (see FIG. 10). 5 g of aqueous PDADMAC solution 1 g of SDS

Dynamic light scattering analysis on the nano-cetaser (Malvern Instruments) revealed an average particle diameter of 200 nm (see FIG. 11).

Claims

claims

1. Nano-hollow capsules obtainable by mixing microemulsions modified with block copolymers.

2. nano hollow capsules according to claim 1, characterized in that the nano hollow capsules have a diameter of 5 nm to 1000 ntn.

3. nano hollow capsules according to any one of claims 1 or 2, characterized in that the microemulsion consists of water, long-chain alcohols and / or an oil component and surfactants.

4. nano hollow capsules according to one of claims 1 to 3, characterized in that the microemulsion is modified with polymers.

5. nano hollow capsules according to claim 4, characterized in that the polymers are water-soluble polyelectrolytes and / or oil-soluble polymers.

6. nanoclaved capsules according to claim 5, characterized in that the polyelectrolytes are selected from water-soluble ionic polymers.

7. nano hollow capsules according to claim 5 or 6, character- ized in that the polyelectrolytes are selected from anionic polyacids, cationic polybases or neutral polyampholytes or polysalts.

8. nanohohlkapseln according to any one of claims 1 to 7, character- ized in that the block copolymers consist of two or more blocks.

9. nanohohlkapseln according to claim 8, characterized in that the blocks of the block copolymers have hydrophilic, polymerizable and / or hydrophobic properties.

10. nanohohlkapseln according to claim 8 or 9, characterized in that the different blocks are characterized in that they are hydrophilic, polymerizable and / or hydrophobic.

11. Nanohohlkapseln according to any one of claims 1 to 10, characterized in that by cross-linking of the polymerizable blocks of the block copolymers, the hollow nanocapsules are coated umhüllend.

12. nanohohlkapseln according to one of claims 1 to 11, characterized in that the nano hollow capsules are pre-filled.

13. nanohohlkapseln according to claim 12, characterized in that the nano hollow capsules are pre-filled with metal salts, metal halides, reducing agents, pharmacologically active substances, magnetically and / or optically active reagents or polymers.

14. nanohohlkapseln according to claim 12 or 13, characterized in that the microemulsion contains metal salts and / or reducing agents.

15. A process for the preparation of nano hollow capsules, according to one of the preceding claims, characterized in that at least two microemulsions are mixed together, which are modified with block copolymers and polymers and

then the resulting nano-hollow capsules worked up.

16. The method according to claim 15, characterized in that one adds inverse microemulsions of water, an oil component and / or long-chain alcohols and surfactants.

17. The method according to claim 15 or 16, characterized in that adding as polymers water-soluble polyelectrolytes for W / O microemulsions and oil-soluble polymers for O / W microemulsions.

18. The method according to claim 17, characterized in that is added as polyelectrolytes, water-soluble ionic polymers.

19. The method according to claim 17, characterized in that is added as polymers anionic from polyacids, cationic polybases or neutral polyampholytes or polysalts.

20. The method according to claim 15, characterized in that is added as polymers oil-soluble polymers and / or oil-in-water microemulsions.

21. The method according to claim 20, characterized in that one adds to the oil-in-water microemulsions electron acceptor and electron donor polymers.

22. The method according to any one of claims 15 to 21, characterized in that block polymers of at least two blocks, the blocks having hydrophilic, hydrophobic and / or polymerizable properties.

23. The method according to any one of claims 15 to 22, characterized in that one adds different blocks, which are characterized in that they are hydrophilic, hydrophobic and / or polymerizable.

24. The method according to any one of claims 15 to 22, characterized in that one crosslinks the polymerizable blocks of the block copolymers, so that the nano hollow capsules are wrapped polymer.

25. The method according to any one of claims 15 to 22, characterized in that prefilled the nano hollow capsules with pharmacologically active substances, magnetically or optically active substances.

26. The method according to any one of claims 15 to 25, characterized in that admixing the microemulsion metal salts, metal halides and / or reducing agents.

27. The method according to any one of claims 15 to 25, characterized in that one fills in a further step, the nano hollow capsules.

28. The method according to claim 27, characterized in that nano hollow capsules filled with metals, metal halides, metal oxides, metal salts, pharmacologically active substances, magnetic, optical or radioactive substances, color pigments or contrast agents.

29. Use of nano hollow capsules, according to any one of claims 1 to 14, for the transport of pharmacologically active substances in the human or animal body.

30. Use of nano hollow capsules, according to one of claims 1 to 14, for the preparation of medicaments for the transport of pharmacologically active substances in the human and animal body.

31. Use of prefilled nano hollow capsules, according to one of claims 1 to 14, as nanoparticles.

32. Use of prefilled nano hollow capsules, according to one of claims 1 to 14, for the coating of surfaces.

33. Use of prefilled nano hollow capsules, according to any one of claims 1 to 14, for incorporation in polymer membranes.