WO2012034696A1 - Photo-stimulatable particle systems, method for producing same, and uses thereof - Google Patents

Photo-stimulatable particle systems, method for producing same, and uses thereof Download PDF

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WO2012034696A1
WO2012034696A1 PCT/EP2011/004622 EP2011004622W WO2012034696A1 WO 2012034696 A1 WO2012034696 A1 WO 2012034696A1 EP 2011004622 W EP2011004622 W EP 2011004622W WO 2012034696 A1 WO2012034696 A1 WO 2012034696A1
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eu
preceding
characterized
nm
nanoparticles
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German (de)
French (fr)
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Miroslaw Batentschuk
Sofia Dembski
Carsten Gellermann
Andres Osvet
Albrecht Winnacker
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Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Friedrich-Alexander-Universität Erlangen-Nürnberg
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B90/00Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
    • A61B90/39Markers, e.g. radio-opaque or breast lesions markers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/57Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • C09K11/572Chalcogenides
    • C09K11/574Chalcogenides with zinc or cadmium
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B90/00Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
    • A61B90/39Markers, e.g. radio-opaque or breast lesions markers
    • A61B2090/3937Visible markers
    • A61B2090/3941Photoluminescent markers
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    • C01P2002/00Crystal-structural characteristics
    • C01P2002/50Solid solutions
    • C01P2002/52Solid solutions containing elements as dopants
    • C01P2002/54Solid solutions containing elements as dopants one element only
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    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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    • C01INORGANIC CHEMISTRY
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    • C01P2004/00Particle morphology
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    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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    • C01P2004/32Spheres
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    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention relates to particle systems that can be stimulated, in particular photo-stimulated, and to the use thereof as luminescent markers for biological and medical diagnostics, as an optically detectable diffusion probe or as a substrate for producing security systems, and as a marking for detecting counterfeits and/or originals.

Description

 Photostimulable particle systems, processes for their preparation and uses

The invention relates to stimulable, in particular photostimulable particle systems and their use as luminescent markers for biological and medical diagnostics, as optically detectable diffusion probe or as a substrate for the production of security systems, as a marker for the detection of plagiarisms and / or originals.

Luminescent nanoparticles (NPs) have great potential for application due to their optical properties. They provide a basis for numerous analytical methods in the field of biology and medical diagnostics or are used to produce security systems for the detection of plagiarism and / or originals. There are different materials available such. B. with organic dyes doped particle systems Base of polymers or oxidic materials, semiconductor NP (Quantum Dots, QDs) or NP based on inorganic phosphors doped with

Rare earth ions [F. Caruso: Colloids and Colloid Assemblies. iley-VCH, Weinheim (2004); W. Tan, S.

Santra, P. Zhang, R. Tapec, J. Dobson: Method for Identifying Cells. Hoffmann US 6924116 B2 (2005); V. Desprez, N. Oranth, J. Sprinke, J.K. Tusa: Nanoparticles for optical sensors, EP 1496126 Bl (2005); A. van Blaaderen, A. Vrij: Synthesis and characterization of colloidal dispersion of fluorescent, monodispenser silica spheres. Langmuir 8, (1992) 2921-2931; R. E. Baily, A. M. Smith, 5. Never: Quantum dots in biology and medicine. Physica E 25, (2004), 1-12; R. Lee, Z. Yaniv: Nanoparticle Phosphorus. WO 03/028061

AI (2003)]. The test methods that can be used often have characteristic limits, which are listed below: · The conventional materials have material-related defects: broad emission spectra, low Stokes shift and / or limited photostability. This is typical of NPs doped with organic dyes.

· Some particle systems, such as B. QDs insist on toxic materials. With regard to in vivo application, even the temporary use of these markers in living organisms is highly questionable.

· Few materials have emission in the biological "optical window" (650-1200 nm) In addition, often the system under study, such as in the case of cell tissue studies, often shows autofluorescence that correlates with the signal from the marker superimposed. Many of the markers used are excited and fluoresce at relatively short wavelengths, where the depth of penetration of the light into the tissue is low.

»As a rule, the stimulating light and the fluorescence are effective at the same time. The signal is weakened by stray light.

One solution could be a time delay of the light emission compared to the excitation. This phenomenon can be observed with phosphorescent materials. For phosphorescent materials, fluorescence decays slowly after stimulation, sometimes for hours or even days. First up to one hour of phosphorescent markers have already been developed and successfully tested on living mice [D. Scherman, M. Bessodes, C. Chaneac, D.L. Gourier, J-P. Jolivet, Q. le Masne, S. Maitrejean, F. Pelle: Persistent luminescent nanoparticles used in the form of a diagnostic agent for in vivo optical imaging. US 2009/0155173 (2009); Q. le Masne, C. Chaneac, J. Seguin, F. Pelle, S. Maitrejean, J-P. Jolivet, D. Gourier, M. Bessodes: Nanoprobes with near-infrared persistent luminescent for in vivo aging. PNAS 104, (2007) 9266-9271].

Based on the known from the prior art materials, it was an object of the present invention to provide nanoparticle systems, which allows the highest possible persistence of stored energy after charging such particles. In addition, the particle systems should be stimulated to stimulated emission by illumination with a targeted light pulse, which may preferably also be in the infrared light range, so that the originally stored energy of such particles can be selectively retrieved when needed.

This object is related to the nanoparticle with the features of claim 1, with respect to a

Nanoparticle system containing a plurality of particles according to the invention, having the features of claim 11, relating to a method for producing a corresponding nanoparticle system having the features of claim 12 and with respect to possible

Uses of such nanoparticle systems with the features of claim 14 solved. The respective dependent claims are advantageous developments.

According to the invention, a nanoparticle is provided which can be converted into an electronically charged state by supplying energy and can be induced to emit electromagnetic radiation by means of stimulation by electromagnetic radiation.

The nanoparticles according to the invention, in particular those of the core-shell type discussed below, are distinguished by the fact that, after being charged with light having a wavelength between 100 and 800 nm, with

X-ray and / or electron beams emitted by stimulated emission by a light pulse having a wavelength between 500 and 1600 nm photons with a wavelength between 400 and 1300 nm.

Surprisingly, in the case of the nanoparticles according to the invention, in particular those of the core-shell type, it has been found that the duration of the light pulse, which can be used for stimulated emission and for retrieving the light energy stored in the charged particle, can be very short, eg approx . 1 or less (A. Winnacker, "X-ray Imaging with

Photostimulable Storage Phosphors and Future Trends. "Physica Medica, Vol. IX (1993), 95-101.) The stimulated emission can be used, for example, by using a laser pulse wherein the energy density of the stimulation laser is about 100 μ / cm 2 or less (R. Schätzing, R. Fasbender, P. Kersten, New High Speed Scanning Technique for Computed Radiography, Proc. SPIE 4682 (2002) 511-520), which provides tremendous advantages over the

Signal to noise ratio, whereby the particles according to the invention are significantly advantageous from those of the prior art, e.g. stand out from the microparticles known from US 2009/0155173.

The particle is characterized by energy storage and thus enabling a time shift between excitation (charge) and detection necessary for background-free detection. For this purpose, the sample to be examined with particulate

Markers that have been charged by exposure to ultraviolet or blue light, or an x-ray pulse prior to examination are marked. Stimulation of the sample with red or infrared (IR) light after minutes or even hours will cause emission in the visible or near-infrared region, ie shorter wavelengths than the excitation light wavelengths. This allows observations of development and transport processes in biological objects over a longer period of time. A specific area can be irradiated with the focused UV or blue light or electron beam, and the charged markers can be detected. The photostimulable phosphors have convincing advantages here: the total stored energy (or, if necessary, only a part of it) can, at the desired later time, be retrieved with an infrared pulse.

As a result, applications are made possible in which the detection of marked objects takes place offset in time from the optical excitation, with the aim of enabling background-free or stray-light-free detection. Separation of charge carriers and their localization

("Trapping") are necessary for phosphorescence and photostimulated luminescence (PSL), but in nanocrystals (NK), the desired stability of trapped electrons / holes may be a problem, if only because of the small distances between the traps recombination through a "tunneling" is possible. The so-called "blinking" of NKs provides an indication of the possibility of charge separation and trapping: with a constant excitation, the luminescence of some NKs is lost, and after some time, it re-emerges.It is known that NKs are charged for During optical excitation, NKs form electron-hole pairs whose recombination leads to light emission.

However, it is possible that one of the two charge carriers leaves the NK. The other charge carrier inside the NK prevents the radiative recombination of the next e-h pairs by Auger relaxation. Measurements with electrostatic force microscopy showed that in CdSe the electron leaves the particle and the hole remains. The particle is again emissive as soon as the electron returns. The "on" and "off" states of NK can take from a few microseconds to minutes. The nature of

Falling is unclear. One suspects the localization the particle surface or on the interface between the core and the shell, in the coupled ligands or in the surrounding matrix. The appearance of the blinking thus confirms the possibility of storing electrons and holes on the nanoscale.

The spatial separation of charge carriers can be improved by the use of two-component semiconductor systems. Such coupled NKs or

Core / shell particles have been designed for a variety of purposes including solar cells and photocatalysts. The generated electrons are accumulated in the semiconductor where the conduction band is deeper, the holes become in the valence band of the other

Semiconductor caught. Examples of such systems are TiO 2 -CdS, ZnO-CdS and SnO 2 -CdSe, CdS-Agl, Cd 3P 2 -TiO 2, Cd 3P 2 -ZnO, AgI-Ag 2S, ZnO-ZnS and ZnSe (core) / CdSe (shell). This design principle can also be used for the shift of the emission spectrum to lower

Energies are used, in which the unwanted scattering of luminescence in biological samples is reduced. Overall, the separate storage of

Electron / holes also feasible on the nanoscale. The targeted nanomarkers will be concerned with bringing these stored charge carriers to radiative recombination thermally or optically (PSL).

The nanoparticles Zn 2 Si0 4 : Mn 2+ considered as an example here obviously have intrinsic traps, which can store charge carriers at room temperature. The traps can be charged with UV light and emptied with red light. This produces the green emission of Mn 2+ . The charging spectrum showed a maximum around 260 nm, which corresponds to an electronic transition from the ground state of the Mn 2+ ion to the conduction band (photoionization).

In particular, it is preferred if the half life ti 2 of the spontaneous decay of the charged state is at least 1 second, preferably at least 1 minute, particularly preferably at least 30 minutes.

Preferred embodiments provide that the transfer into the electronically charged state takes place by means of electromagnetic radiation, preferably by electromagnetic radiation having a wavelength between 100 and 800 nm, in particular UV radiation, and / or by X-radiation and / or by electron beams.

The radiation used to stimulate the emission may have a wavelength between 200 to 2000 nm, preferably between 400 to 1600 nm.

The wavelength of the emission is preferably between 200 to 4000 nm, preferably 400 to 1600 nm.

Preferred particle sizes are between 2 to 1000 nm. It is further preferred if the nanoparticle is present as a core-shell nanoparticle. Likewise, however, there is the possibility that the nanoparticle is designed as a "full particle".

Thus, preferably, a stimulable nanoparticle is provided which can be converted into an electronically charged state by light of a wavelength between 100 and 800 nm and / or with X-rays or electron beams, and by a light pulse can be excited with a wavelength of photons between 500 and 1600 nm for the emission of light of a wavelength between ¬ 400 and 1300 nm. According to the invention, a stimulable nanoparticle is further provided,

a) the one amorphous core of silica or a compound selected from the group consisting of silica, silicates, vanadates, tungstates, phosphates, oxides, sulfides, sulfates, aluminates and / or halides, such. Fluorobromides, a first main group, transition or

 lanthanide metal,

b) one applied on the amorphous core

 stimulable shell containing at least one

A compound selected from the group consisting of silica, silicates, vanadates, tungstates, phosphates, oxides, sulfides, sulfates, aluminates and / or halides, e.g. Fluorobromides, a first main group, transition or

 Lanthanide metal doped with transition metal or lanthanide metal ions of at least a second variety of a transition metal or lanthanide metal other than the first main group metal, transition metal or lanthanide metal, wherein

the diameter of the silica core between 10 and

290 nm, preferably between 10 and 260 nm, more preferably between 10 and 50 nm or 75 and 260 nm.

The above-mentioned compound may include main group, transition or lanthanide metals of all the groups of the Periodic Table of the Elements. To the compounds of a first main group metal Thus, among others, Ca and Sr compounds are to be counted.

A preferred embodiment provides that the second grade of transition metal or lanthanide metal ions used for the doping is selected from the group consisting of Pb 2+ , Mn 2+ , Cu + , Dy 3+ , Sm 3+ , Eu 2+ , Eu 3+ , Tb 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Gd 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ and / or Combinations of this.

It is likewise preferred if the compound forming the core and / or the shell-forming compound or the shell-forming compound is independently selected from the group consisting of MgSiO 3 , Zn 2 SiO 4 ,

ZnMgSi 2 0 6 , CaMgSi 2 0 6 , Sr 2 MgSiO 7 , SrAl 2 0 4 , CaAl 2 0 4 , YV0 4 , GdV0 4 , NaGd (W0 4 ) 2 , CaW0 4 , Y 2 0 3 , LaP0 4 , ZnS , CaS, BaFBr and / or combinations thereof.

In particular, the following doped materials are suitable as a constituent of the core and / or the shell or as the total material of the core and / or the shell:

Zn 2 Si0 4 : Mn, YV0 4 : Dy J + / Sm, NaGd (W0 4 ) 2 : Eu,

NaGd (W0 4 ) 2 : Eu 3+ , CaW0 4 : Eu 3+ / Tb 3+ , YV0 4 : Eu 3+ , Y 2 0 3 : Eu 3+ ,

GdV0 4 : Eu 3+ , CaP0 4 : Ce 3+ / Tb 3+ , ZnS: Cu 1+ / Pb 2+ , CaS: Eu 2+ / Sm 3+ , BaFBr: Eu 2+ , ZnMgSi 2 0 6 , CaMgSi 2 0 6 and MgSi0 3 , wherein the last three mentioned silicates are doped with manganese, europium or dysprosium ions and Sr 2 MgSi 2 0 7 , which is doped with europium and / or dysprosium ions, and the silicate Ca 0 , 2 Zn 0 , 9 g 0 , 9Si 2 0 6 doped with Eu 2+ , Dy 3+ and / or Mn 2+ .

Further examples are: CaS: Ln (with Ln, Ce, Sm, Eu), Silicates Zn 2 Si0 4 doped with Mn or Lnl, Ln2 (with Ln (l, 2): Ce 3+ , Eu 3+ , Tb 3+ , Sm 3+ , as an alternative

Y 2 Si0 5 : Eu 3+ , Ce 3+ Tb 3+

Aluminates (Sr, Ca) Al 2 O: Ln (with Ln: Ce 3+ , Pr 3+ , Nd 3+ , Eu 2+ / Eu 3+ , Tb 3+ , Dy 3+ , Er 3+ )

 ZnS: Cu, Pb and different calcium phosphates.

Specific examples of luminescent materials which are suitable for core and / or shell are, for example: (very hygroscopic); CsI: Tl; CsI: Na; LiF: Mg;

LiF: g, Ti; LiF: Mg, Na; KMgF 3 : Mn; BaFCl: Eu; BaFCl: Sm; BaFBr: Eu; BaFCl 0 , sBr 0 , 5 : Sm; BaY 2 F 8 : A (A = Pr, Tm, Er, Ce); BaSi 2 0 5 : Pb; BaMg 2 Ali 6 0 27 : Eu; BaMgAli 4 0 23 : Eu;

BaMgAli 0 Oi 7 : Eu; BaMgAl 2 0 3 : Eu; Ba 2 P 2 O 7 : Ti;

(Ba, Zn, Mg) 3 Si 2 0 7: Pb; Ce (Mg, Ba) Al u 0i 9 ;

Ceo, 65Tb 0l 35MgAliiOi9: Ce, Tb; MgAludg: Ce, Tb; MgF 2 : Mn;

MgS: Eu; MgS: Ce; MgS: Sm; MgS: (Sm, Ce); (Mg, Ca) S: Eu;

MgSiO 3 : Mn; 3.5MgO x 0.5MgF 2 x Ge0 2 : Mn; MgW0 4 : Sm;

MgW0 4 : Pb; 6MgO x As 2 0 5 : Mn; (Zn, Mg) F 2 : Mn; (Zn 4 Be) S0 4 : Mn; Zn 2 Si0 4 : Mn; Zn 2 Si0 4 : Mn, As; Zn 3 (PO 4 ) 2 : Mn; CdB0 4 : Mn;

CaF 2 : Mn; CaF 2 : Dy; CaS: A (A = lanthanide, Bi);

(Ca, Sr) S Bi; CaW0 4 : Pb; CaW0 4 : Sm; CaSO 4 : A (A = Mn, lanthanide); 3Ca 3 (PO 4 ) 2 x Ca (F, Cl) 2 : Sb, M n ; CaSiO 3 : Mn, Pb; Ca 2 Al 2 Si 2 O 7 : Ce; (Ca, Mg) Si0 3: Ce; (Ca, Mg) Si0 3 : Ti; 2SrO x 6 (B 2 O 3 ) x SrF 2 : Eu; 3Sr 3 (PO 4 ) 2 CaCl 2 : Eu; A 3 (P0 4 ) 2

ACl 2 : Eu (A = Sr, Ca, Ba); (Sr, Mg) 2 P 2 0 7 : Eu;

(Sr, Mg) 3 (PO 4 ) 2 Sn; SrS: Ce; SrS: Sm, Ce; SrS: Sm; SrS: Eu; SrS: Eu, Sm; SrS: Cu, Ag; Sr 2 P 2 O 7 : Sn; Sr 2 P 2 0 7 : Eu;

Sr 4 Al 14 O 25 : Eu; SrGa 2 S 4 : A (A = lanthanide, Pb);

SrGa 2 S 4 : Pb; Sr 3 Gd 2 Si 6 O 8 : Pb, Mn; YF 3 : Yb, He; YF 3 : Ln (Ln =

Lanthanide); YLiF 4 : Ln (Ln = lanthanide); Y 3 Al50 12 : Ln (Ln = lanthanide); YAI 3 (B0 4) 3 Nd, Yb; (Y, Ga) B0 3 : Eu;

(Y, Gd) B0 3 : Eu; Y 2 Al 3 Ga 2 O 12 : Tb; Y 2 Si0 5 : Ln (Ln = lanthanide); Y 2 0 2 S: Ln (Ln = lanthanide); YV0 4 A (A = lanthanide, In); Y (P, V) 0 4 : Eu; YTa0: Nb; YAI0 3 : A (A = Pr, Tm, Er,

Ce); YOCl: Yb, Er; LnP0 4 : Ce, Tb (Ln = lanthanide or mi lanthanides); LuV0 4: Eu; GdV0 4 : Eu;

Gd 2 0 2 S: Tb; Gd gB 5 Oi 0 : Ce, Tb; LaOBr: Tb; La 2 0 2 S: Tb;

LaF 3 : Nd, Ce; BaYb 2 F 8 : Eu; NaYF: Yb, He; NaGdF: Yb, Er; NaLaF 4 : Yb, Er; LaF 3 : Yb, Er, Tm; BaYF 5 : Yb, He; GaN: A (A = Pr, Eu, Er, Tm); Bi Ge 3 0i 2 ; LiNb0 3: Nd, Yb; LiNb0 3 : He; LiCaAlF 6 : Ce; LiSrAlF 6 : Ce; LiLuF: A (A = Pr, Tm, Er, Ce); Li 2 B 4 O 7 : Mn; Y 2 0 2 Eu; Y 2 Si0 5 : Eu; CaSi0 3 : Ln, where Ln = 1, 2 or more lanthanides.

M I X: xBi with M 1 = Rb and X = Cl, Br and / or I

RbX: xTl with X = Br and / or Cl and / or I

YOXrzA with X = Cl and / or Br, and A = Ce or Tb

When classified according to the host lattice type, the following preferred embodiments are also included:

1. halides: eg XY 2 (X = Mg, Ca, Sr, Ba; Y = F, Cl, J); CaF 2 : Eu (II); BaF 2 : Eu; BaMgF 4 : Eu;

LiBaF 3 Eu; SrF 2 Eu; SrBaF 2 Eu; CaBr 2 Eu-Si0 2 ;

CaCJ 2 : Eu; CaCJ 2 : Eu-Si0 2 ; CaCJ 2 : Eu, Mn-Si0 2 ;

CaJ 2 : Eu; CaJ 2 : Eu, Mn; KMgF 3 : Eu; SrF 2 : Eu (II);

BaF 2 : Eu (II); YF 3 ; NaYF 4 ; MgF 2 : Mn; MgF 2 : Ln (Ln = lanthanide (s)).

KBr: In +

RbBr: Ga, CsBr: Ga, RbBr: Eu 2+, CsBr: Eu 2+,

Cs 2 NaYF 6 : Ce 3+ , CsNaYF 6 : Pr 3+

CaF 2 : Eu 3+ (or Eu 2+ ), Sm 3+ ,

2. alkaline earth sulfates: eg XS0 4 (X = Mg, Ca, Sr,

Ba); SrS0 4 : Eu; SrS0 4 : Eu, Mn; BaS0 4 : Eu;

BaS0 4 : Eu, Mn; CaSO 4 ; CaS0 4 : Eu; CaSO 4 : Eu, Mn; and mixed alkaline earth sulfates, also in combination with magnesium, eg Ca, MgS0 4 : Eu, Mn. 3. phosphates and halophosphates: eg CaP0 4 : Ce, Mn; Ca 5 (PO 4 ) 3 Cl: Ce, Mn; Ca 5 (PO 4 ) 3 F: Ce, Mn; SrP0 4 : Ce, Mn; Sr 5 (PO 4 ) 3 Cl: Ce, Mn; Sr 5 (PO 4 ) 3 F: Ce, Mn; the latter also codoped with Eu (II) or codoped with

Eu, Mn; -Ca 3 (PO 4 ) 2 : Eu; β-Ca 3 (PO 4 ) 2 : Eu, Mn;

Ca 5 (P0 4 ) 3 Cl: Eu; Sr 5 (P0 4) 3, C1: Eu; Ba 10 (P0 4 ) 6 C1: Eu;

Bai 0 (PO 4 ) 6 Cl: Eu, Mn; Ca 2 Ba 3 (P0 4 ) 3 C1: Eu;

Ca 5 (PO 4 ) 3 F: Eu 2+ X 3+ ; Sr 5 (PO 4 ) 3 F: Eu 2+ X 3+ (X = Nd, Er,

Ho, Tb); Ba 5 (P0 4 ) 3 C1: Eu; β-Ca 3 (PO 4 ) 2 : Eu;

CaB 2 P 2 O 9 : Eu; CaB 2 P 2 O 9 : Eu; Ca 2 P 2 O 7 : Eu; Ca 2 P 2 O: Eu, Mn;

Srio (PO 4 ) 6 Cl 2 : Eu; (Sr, Ca, Ba, Mg) i0 (P0 4) 6 C1 2: Eu;

LaP0 4 : Ce; CeP0 4 ; LaP0 4 : Eu; LaP0 4 : Ce; LaP0 4 : Ce, Tb;

CePO 4 : Tb;

Zn 3 (PO 4 ) 2 : Mn 2+ (Zn 3 (PO 4 ) 2 : Mn 2+ , Al 3+ Zn 3 (PO 4 ) 2 : Mn + , Ga 3+ Sr 3 (PO 4 ) 2 : Eu 2+ , Sr 5 (P0 4 ) 3 : Eu 2+ , Sr 2 P0 4 : Eu 2+

4. Borates: eg LaB0 3 ; LaB0 3 : Ce; ScB0 3 : Ce; YAIBO 3 : Ce;

YB0 3 : Ce; Ca 2 B 5 0 9 Cl: Eu; xEuO x yNa 2 0 x eg 2 0 3 .

Sr 2 B0 3 X: Eu 2+ with X = Cl, Br and / or I

Sr 2 _ x (B 5 O 9) 5-y / 2 X y : D x where X = halides and D =

Eu 2+ , Ce 3+

5. Vanadates: eg YV0; YV0 4 : Eu; YV0 4 : Dy; YV0 4 : Sm;

YV0 4 : Bi; YV0 4 : Bi, Eu; YV0 4 : Bi, Dy; YV0 4 : Bi, Sm;

YV0 4 : Tm; YV0 4 Bi, Tm; GdV0 4 ; GdV0 4 : Eu; GdV0 4 : Dy;

GdV0 4 : Sm; GdV0: Bi; GdV0 4 : Bi, Eu; GdV0 4 : Bi, Dy;

GdV0 4 : Bi, Sm; YV0 4 : Eu; YV0 4 : Sm; YV0 4 : Dy.

6. aluminates: eg MgAl 2 O 4 : Eu; CaAl 2 0 4 : Eu; SrAl 2 0 4 Eu;

BaAl 2 0 4 : Eu; LaMgAluOig: Eu; BaMgAli 0 Oi 7 : Eu; BaMGalioOi 7 : Eu, Mn; CaAli 2 0 19 : Eu; SrAli 2 0i 9 : Eu;

SrMgAlioOi 7 : Eu; Ba (A1 2 0 3 ) 6 : Eu; (Ba, Sr) MgAl 10 Oi 7 : Eu, n; CaAl 2 O 4 : Eu, Nd;

SrAl 2 0 4 Eu, Dy; Sr 4 Ali 4 0 25 : Eu, Dy.

MA1 2 0 4 (M = Ca, Sr, Mg, Ba), in particular BaAl 2 0 4; Sr 5 Al 8 0 7 (doped with Eu and Dy).

Aluminosilicates CaSrAlSi0 7 and Ca 2 Al 2 Si0 7 (also with Eu, Dy-doping). 7. silicates: eg BaSrMgSi 2 0 7 : Eu; Ba 2 MgSi0 7 : Eu;

BaMg 2 Si 2 O 7 : Eu; CaMgSi 2 0 6 : Eu; SrBaSi0 4 : Eu; Sr 2 Si 3 O 8 x SrCl 2 : Eu; Ba 5 Si0 4 Br 6: Eu; Ba 5 Si0 4 Cl 6 : Eu;

Ca 2 MgSi 2 0 7: Eu; CaAl 2 Si 2 O 8 : Eu; Cai, 5 Sr 0 , sMgSi 2 0 7 : Eu; (Ca, Sr) 2 MgSi 2 0 7 : Eu; Sr 2 LiSi0 4 F: Eu; Sr 3 Al 2 O 6 : Eu, Sr 3 Al 2 O 6 : XY (X = Eu, Y = Dy), Sr 5 Al 2 O 8 : Eu, Y 3 Al 5 O 2 : Ce,

Gd 3 Al 5 O 2 : Ce, Lu 3 Al 5 O 2 : Ce and (GdLu) 3 Al 5 O 2 : Ce, Tb 3 Al 5 O 2 : Ce, Tb 3 Al 5 O 2 : XY (X = Ce , Y = Eu, Mn),

Mg 2 Si0 4 : Mn 2+ , Dy 3+ and M 3 MgSi 2 O 8 (M = Ca, Sr, Ba). Mg 2 Si0 4 : Mn 2+ , Dy 3+ ; M 3 MgSi 2 O 8 (M = Ca, Sr, Ba).

ZnMgSi 2 0 6 , CaMgSi 2 0 6 , MgSiO 3 (doped with Eu, Mn, Dy) Sr 2 MgSi 2 0 7 (doped with Eu, Dy)

Sr 2 M II Si 2 O 7 : Ce 3+

Sr 5 Si0 4 X 6: Eu 2+ with X = halides

Y 2 Si0 5 : X with X = Tb and / or Ce

Y 2 Si0 5 : Ce 3+ , Sm 3+

8. tungstates and molybdate: eg X 3 W 0 6 (X = Mg, Ca, Sr, Ba); X 2 W0 4 (X = Li, Na, K, Rb, Cs); XMo0 4 (X =

Mg, Ca, Sr, Ba) and MgW0 4 , CaW0 4 , CdW0 4 , ZnW0 4 ; and polymolybdates or polytungstates or the salts of the corresponding hetero- or isopolyacids.

9. germanates: eg Zn 2 Ge0 4 . 10. In addition, the following classes: ALn0 2 : Yb, Er (A = Li, Na / Ln = Gd, Y, Lu); LnA0: Yb, Er (Ln = La, Y; A = P, V, As, Nb); Ca 3 Al 2 Ge 3 O 2: E; Gd 2 0 2 S: Yb, He;

La 2 S: Yb, Er, Ba 2 ZnS 3 : Ce.

All of the aforementioned materials are also suitable for the preparation of nanoparticles that are not in the core-shell type, i. have only one phase ("full particles").

In the case of the nanoparticles according to the invention, it is further preferred that the doping concentration of the at least one second, different from the first transition metal or lanthanide metal based on the

Amount of the first transition or Lanthanidmetalls between 0.01 and 25 mol%, preferably between 0.5 and 20 mol%, more preferably between 1 and 10 mol%, particularly preferably between 2 and 7.5 mol% , The indicated concentrations of

Doping also applies in particular to the materials explicitly mentioned in the last paragraph.

In a further preferred embodiment, the surface of the shell is functionalized with functional groups, these functional groups being in particular selected from the group consisting of amino, carboxylate, carbonate, maleic, imine, imide, amide, Aldehyde, thiol, isocyanate, isothiocyanate, acylazide, hydroxyl, N-hydroxy-succinimide ester, phosphate, phosphonic acid, sulfonic acid, sulfonyl chloride, epoxy, CC double bond-containing groups such as (meth) acrylic acid or (meth) acrylate or norbornyl groups. Further preferred embodiments provide that the particle surface is surrounded by a shell of silica, polymer, aluminum oxide or polyethylene glycol, TiO 2 , ZnO, ZrO 2 , the surface of the PLS particle is chemically modified.

It is likewise advantageous if the surface has covalently or noncovalently bound compound molecules and / or reactive groups.

In addition, it is possible that, as the connecting molecule, one or more chain-like molecules having a polarity or charge opposite to the surface of the nanoparticles are non-covalently bonded to the surface of the particles, the chain-shaped molecules are anionic, cationic or zwitterionic detergents, acidic or basic proteins, Polyamides or polysulfone or polycarboxylic acids may be.

It is furthermore advantageous if the surface and / or the connecting molecules connected to the surface of the nanoparticles have reactive neutral, charged or partially charged groups such as amino groups, carboxylic acid groups, thiols, thioethers, disulfides, imidazoles, guanidines, hydroxyl groups, indoles, vicinal diols, aldehydes, alpha-haloacetyl groups, N-maleimides, mercury organyls, aryl halides, acid anhydrides, isocyanates, isothiocyanates, sulfonic acid halides, imido esters, diazoacetates, diazonium salts, 1,2-diketones, alpha-beta-unsaturated carbonyl compounds, azolides, silanes, phosphonic acids, phosphoric acid esters or derivatives of said groups, said reactive groups allowing chemical bonding with further compound molecules or affinity molecules. The nanoparticles of the invention may be oriented ¬ equipped also with one or more affinity molecules or a plurality of mutually coupled affinity molecules, which affinity molecules can on the one hand bind to the particle surface and on the other hand to bind to a biological or other organic substance.

The affinity molecules can e.g. monoclonal or polyclonal antibodies, proteins, peptides, oligonucleotides, plasmids, nucleic acid molecules, oligo- or polysaccharides, haptens such as biotin or digoxin, or a low molecular weight synthetic or natural antigen.

It is also possible that the affinity molecule is covalently or non-covalently coupled to the particle through reactive groups on the affinity molecule and on the simple detection probe.

The reactive groups on the surface of the affinity molecule may be selected from amino groups, carboxylic acid groups, thiols, thioethers, disulfides, imidazoles, guanidines, hydroxyl groups, indoles, vicinal diols, aldehydes, alpha-haloacetyl groups, N-maleimides, mercury organyls, aryl halides, acid anhydrides, isocyanates , Isothiocyanates,

Sulfonic acid halides, imido esters, diazoacetates, diazonium salts, 1,2-diketones, alpha-beta-unsaturated carbonyl compounds or azolides.

There may be a covalent or non-covalent, self-assembled compound between the PSL particle and the affinity molecule. According to the invention is also a stimulable

Nanoparticle system provided, which contains a plurality of the aforementioned nanoparticles. The polydispersity of the nanoparticles in the nanoparticle system according to the invention is preferably between 0.1 and 10%, preferably between 1 and 3%.

According to the invention, a process for the preparation of a nanoparticle system described above is also disclosed in which amorphous core particles

Silica or a compound selected from the group consisting of silica, silicates, vanadates, tungstates, phosphates, oxides, sulfides, sulfates, aluminates and / or halides, e.g. Fluorobromo-, a first main group, transition or

Lanthanide metal, with a mean diameter between 10 and 290 nm by wetting with an aqueous solution containing

a) at least one sort of ions of a first

 Transition metal or lanthanide metal,

b) at least one sort of ions of a second, from

 first different transition metal or

 Lanthanide metal as well

c) in the event that the shell is vanadate,

 It is intended that vanadium, tungstate, phosphate, sulfide and / or halide ions, in particular fluoride and bromide ions, be coated with olframates, phosphates, sulfides, sulfates, aluminates and / or halides and then the coated core particles are tempered become.

In order to obtain the preferred concentrations of the dopants specified above, the molar ratios of the second grade of transition metal or lanthanide metal to the first grade of transition metal or lanthanide metal are preferably set accordingly. The aqueous solution used can be further additives, such as

a) an organic carboxylic acid having at least two acid functionalities, preferably citric acid, and / or

b) an alcohol having at least two alcohol functionalities, preferably polyethylene glycol and / or polypropylene glycol

contain.

The step of tempering is preferably carried out at temperatures between 500 to 1500 ° C, preferably 700 to 1300 ° C, more preferably at 800 to 1200 ° C, in particular at 1000 ° C to 1100 ° C.

It is likewise preferred if removal of the solvent, preferably by lyophilization of the particles, is carried out after wetting and before the sintering step.

A further preferred embodiment provides that after the tempering step, a chemical modification of the surface of the PSL particles and / or production of reactive groups on the surface of the particles and / or connection of one or more compound molecules with the surface of the PSL particles by covalent or non-covalent bond.

After the tempering step, further surface modification of the particles with an amino silane compound and / or with an amino, carboxylate, carbonate, maleic, imine, imide,

Amide, aldehyde, thiol, isocyanate, isothiocyanate,

Acylazide, hydroxyl, N-hydroxy-succinimide ester, Phosphate, phosphonic acid, sulfonic acid, sulfonic acid chloride, epoxy, cc double bond-containing, such as (meth) acrylic acid or (meth) acrylate or norboryl-containing compound. For example, TRIAMO (N- [3 [trimethoxysilyl) -propyl] diethylenetriamine) can be used for this purpose.

According to the invention, uses of the above-described nanoparticle system are also indicated. In particular, the nanoparticle systems according to the invention are suitable as a diagnostic agent and / or as a marker, in particular for biological or medical applications; as an optically detectable diffusion probe; in security systems; as a substrate for security systems and / or as markers for the detection of originals and / or plagiarisms and / or as contrast agents for biomedical applications and means for forensic investigations. When using the nanoparticle system according to the invention, it is preferred if the nanoparticle system is brought into an electronically charged state with light having a wavelength between 100 and 800 nm, with X-rays and / or electron beams, and by means of a light pulse having a wavelength between 400 and 1600 nm for the stimulated emission of photons with a wavelength between 500 and 1600 nm is excited. The light pulse used to stimulate the emission preferably has the following characteristics:

a) a duration between 10 ns and 1 min, preferably

 between 100 ns and 100 s, more preferably between 250 ns and 10 ps, in particular between

500 ns and 3 s and / or b) has an energy density between 0.01 pJ / cm 2 and 100 pj / cm 2 , preferably between 0.1 pJ / cm 2 and 20 pj / cm 2, more preferably between 1 pj / cm 2 and 10 pj / cm 2 .

It can also be used continuous radiation for stimulation. It is preferred that the power density of the beam is between 0.01 W / cm 2 and 100 W / cm 2 , more preferably between 1 W / cm 2 and 10 W / cm 2 .

These luminescent particle systems are particularly suitable as photostimulable markers for biological and medical diagnostics, as optically detectable diffusion probes for the production of

Security systems and as markers for the detection of plagiarism / originals.

The following examples illustrate the potential applications of PLS particles.

The protein A may have special biological functionality, for example the ability to open the pores of the cell membrane. It should be clarified whether it is with regard to this

Function differs from a protein B. For this purpose, one half of the nanoparticles to be added to a cell structure will be functionalized with protein A, the other half with protein B. The binding of proteins to the nanoparticles is carried out by an appropriate surface modification of the particles, as described in more detail below. The first half (functionalized with A) is now additionally "marked" in such a way that it is made PSL-capable by charging

Cell grouping for the expected reaction time to all na- exposed to noparticles. If the PSL is then triggered by the irradiation of IR light, only the PSL-capable particles, ie only those that have been functionalized with protein A, can be seen in the luminescence of the nanoparticles, since only these were charged. But if one stimulates the photoluminescence, then one sees both particle types, thus the B marked ones. Different spatial distributions of luminescence in PSL and photoluminescence (PL) excitation (in cell wall and cell interior) therefore indicate the different biological activity of the two proteins.

Another example is the charging of the messenger substance of a synapse fixed to a PSL-capable NP via appropriate functionalization and the observation of the subsequent distribution and the temporal and spatial extension.

Such optical "tagging" allows diffusion and transport processes with very high spatial resolution in vivo and in vitro.

Particularly preferred examples of the materials which can be used according to the invention as shell are described below, but other materials than those explicitly mentioned here can also be used.

ZnS: Cu + , Pb 2+

Zinc sulfide doped with Cu + and Pb 2+ is a phosphorescent phosphor [S. Shionoya, WM Yen.

Phosphorus Handbook. [Ed.] GHKG. sl: CRC Press, 1999. TZU], which also shows PSL (photostimulable luminescence) and as a storage phosphor for the Visualization of infrared (IR) lasers is used [www.phosphor-technology.com]. Accordingly, a ZnS: Cu + , Pb 2+ marker charged with UV or blue light can be made to glow in the visible region of the spectrum after a time interval by an IR pulse. The luminescence mechanisms of ZnS are particularly well studied: Cu + : Green luminescence with a broad band at A max = 520 nm is a donor-acceptor emission, with both Cl ~ and Al 3+ ions inserted through the preparation Donors can serve.

Different lattice defects in ZnS can localize electrons and holes and thus contribute to phosphorescence. The duration of the afterglow can be significantly increased by the creation of deep traps with co-ions.

The PSL in ZnS: Cu + , Pb 2+ comes about through the release of electrons from the traps [DE Mason. Rev. Modern Phys. 1965, vol. 37, p. 743; R. Scheps, F. Hanson. J. Appl. Phys. 1985, Vol. 57, p. 610]. The traps are stable at room temperature, thus the IR-stimulated luminescence can be observed even after a few hours [. Sidran. Appl. Optics. 1969, Vol. 8, p. 79; E. Bulur, HY Göksü. phys.

stat. Sol. A. 1997, Vol. 161, p. R9].

ZnS: Eu, Mn

The UV-excited luminescence of nanocrystalline ZnS: Eu, Mn is also sensitive to IR light [Chen, W. US Pat. No. 7,126,126 Oct. 24. 2006]. This effect is due to a charge transfer Eu 3+ + n 2+ <-> Eu 2+ + Mn 3+ between the two dopant ions linked and proved that also Eu and Mn act as traps for charge carriers.

CaS: Eu, Sm

The materials system CaS shows a very good agreement with the requirement profile: Eu, Sm, an effective IR converter with fast reaction time [Y. Tamura, A. Shibukawa. Jap. J. Appl. Phys. 1993, Vol. 32, 7, pp. 3187-3196]. The emission maximum lies in the red spectral range, the stimulation spectrum extends from 900 to 1500 nm. However, CaS is slightly water-soluble, but this disadvantage can be overcome by sheathing the CaS microparticles with Si0 2 , Ti0 2 [C. Guo, B. Chu, M. Wu, Q. Su. J. Lumin.

2003, Vol. 105, 2-4, pp. 121-126], or CaF 2 [C.-F.

Guo, B.-L. Chu, J. Xu, Q. Su. Cehm. Res. Chinese U.

2004, Vol. 20, 3, pp. 253-257]. The PSL mechanism is well-informed in this material system and should be given as an example a bit more detailed here:

The current models of charge, storage of energy and charge carriers and the stimulated emission essentially go back to the end of the

50s model of stimulated emission in SrS: Eu, Sm [S.P. Cellar, G.D. Pettit. Phys. Rev. 1958, Vol. 111, 6, pp. 1533-1539; S. P. Basement, cellar.

Phys. rev. 1959, vol. 113, 6, p. 1415; S.P. Keller, J.E. Mapes, and G. Cheroff. Phys. Rev. 1957, vol. 108,

3, pp. 663-676]. It has been modified by the newer authors [Y. Tamura, A. Shibukawa. Jap. J. Appl.

Phys. 1993, Vol. 32, 7, pp. 3187-3196; Y. Tamura. Jap. J. Appl. Phys. 1994, Vol. 33, pp. 4640-4646; J. Wu, D. Newman, I.V. F. Viney. Appl. Phys. B. 2004, vol. 79, p.

239-243; J. Wu, D. Newman, and IVF Viney. J. Lu minute 2002, Vol. 99, 3, pp. 237-245; M. Danilkin, et al. Radiation Measurements. 1995, Vol. 24, 4, pp. 351-354; M. Weidner, A. Osvet, G. Schierning, M. Batentschuk, A. Winnacker. Journal of Applied Physics. 2006 Bd. 100, 7, p. 073701]. By irradiation with high-energy light (blue, UV), part of the Eu 2+ ions can be ionized to Eu 3+ . These Eu ions in trivalent valence state are called hole traps. The excited into the conduction band electrons of Sm 3+ ions bound (Sm 3 + ions are reduced to Sm 2+). The resulting electron traps or

Hole traps (Eu 3+ ) are stable at room temperature, some of the charge carriers are stored in the traps for several hours.

When the charged CaS: Eu, Sm is stimulated with low-energy IR light in the range of 900-1500 nm, the red luminescence of Eu 2+ is shown . By stimulating light the electrons stored at the Sm 2+ can be excited back into the conduction band and recombine with a hole stored at the Eu 3+ . As a result, the Eu 3+ ions are returned to the bivalent valence state. The resulting Eu 2+ is in the excited state and changes to the ground state, emitting the characteristic luminescence.

Zn 2 SiQ 4 : Mn 2+ and ZnMgSi 2 Q 6 : Mn 2+ , Eu 2+ , Dy 3+ Optoelectronics use numerous silicate-based phosphors, including one of the oldest phosphors, Zn 2 Si0 4 doped with n 2 + , which has both phosphorescence and PSL properties. The usual method of preparation is solid-state synthesis [p. Shionoya, WM Yen. phosphorus

Handbook. [Ed.] GHKG. sl: CRC Press, 1999. TZU ]. The green luminescence (A max = 520 nm) of the manganese in a-Zn 2 Si0 4 (illemite) and the red-orange (A max . = 600 nm) in β-Zn 2 Si0 4 is due to the intraionic dd junctions in Mn 2+ . In Zn 2 Si0 4 : Mn at least two types of traps were found from which the electrons can return to the Mn ion by tunneling, which in turn leads to phosphorescence [P. Thioulouse, IF Chang, EA Giess. J. Electrochem. Soc. 1983, Vol. 130, p. 2065]. Also, irradiation with a He-Ne laser (633 nm) leads to the liberation of the stored electrons from the traps and subsequent PSL in the region of the emission of Mn + ions. The PSL effect has also been observed in Ga-doped zinc silicates [H. Hess, phys. Status solidi (a). 1984, Vol. 85, p. 543].

About MgSi0 3 and ZnMgSi 2 0 6 , both doped with

Mn 2+ , Eu 2+ , Dy 3+ , was reported in [XJ. Wang, D. Jia, WM Yen.

J. Lumin. 2003, Vol. 102-103, pp. 34-37] or in [D. Scherman, M. Bessodes, C. Chaneac, D.L. Gourier, J-P.

Jolivet, Q. le Masne, S. Maitrejean, F. Pelle. Patent application WO 2007/048856 AI, published 03.05.2007. Q. le Masne, C. Chaneac, J. Seguin, F. Pelle, S.

Maitrejean, JP. Jolivet, D. Gourier, M. Bessodes. PNAS 2007, Vol. 104, p. 9266]. These phosphors emit in the red region (A max. = 650 nm) and show a long-life (several hours) phosphorescence. A shift of the emission spectrum in the near-infrared can be achieved with a partial replacement of Zn and Mg by Ca [D. Scherman, M.

 Bessodes, C. Chaneac, D.L. Gourier, J-P. Jolivet, Q. le Masne, S. Maitrejean, F. Pelle. Patent application WO 2007048856 AI, published 03.05.2007. Q. le Masne, C. Chaneac, J. Seguin, F. Pelle, S. Maitrejean, J-P.

Jolivet, D. Gourier, M. Bessodes. PNAS 2007, Vol. 104,

P. 9266]. SrAl 2 0 4 : Er + , Dy J and Sr 3 Al 2 Q 6 : Eu, Dy J

Have alkaline earth aluminates prepared as doped powders, ceramics or single crystals suitable for the

Objectives of the project necessary properties. The most widely used phosphor in this group is SrAl 2 0 4 : Eu 2+ , Dy 3+ , which has become clearer than previously used due to its excellent and long-lasting phosphorescence

ZnS: Cu, Co has prevailed. As material showing effective green luminescence (A max = 520 nm), SrAl 2 O 4 : Eu 2+ has been known since 1966 [H. Long. US Patent 3,294,699] and has been systematically studied by Blasse and Bril [G. Pale, A. Bril. Philips Res. Rep.

 1968, Vol. 23, p. 201]. The phosphorescence of

SrAl 2 0 4 : Eu 2+ is formed after prolonged irradiation with UV light [V. Abbruscato. J. Electrochem. Soc.

1971, vol. 118, 6, p. 930]. In [T. Matsuzawa, Y. Aoki, N. Takeuchi, Y. Murayama. J. Electrochem. Soc. 1996

Vol. 143, 8, p. 2670], it has been shown that the phosphorescence of SrAl 2 O 4 : Eu 2+ can be substantially improved by co-doping with trivalent rare earth ions (SE). In [H. Aizawa, T. Katsumata, J. Takahashi, K. Matsunaga, S. Komuro, T. Morikawa.

Rev. Sei. Inst. 2003, vol. 74, 3, p. 1344], it was found that the maximum storage efficiency of SrAl 2 O 4 : Eu is achieved by doping with Dy 3+ . A model for the phosphorescence of CaAl 2 O 4 : Eu 2+ , SE 3+ , is reported in [T. Aitasalo, P. Deren, J. Hölsä, H.

Jungner, J.-C. Krupa, M. Lastusaari, J.

Legendziewicz, J. Niittykoski, W. Strek. J. Sol. St. Chem. 2003, Vol. 171, pp. 114-122], in which oxygen or calcium vacancies are proposed as traps for electrons and holes. The trapped charge carriers can also be filled with light Sr (Ca) A1 2 0 4 : Eu, Dy stimulate (PSL) [W. Jia, H. Yuan, S. Holmstrom, H. Liu, WM Yen. J. Lumin. 1999, vol. 83/84, p. 465], [T. Aitasalo, J. Hölsa, H. Jungner, M. Lastusaari, J. Niittykoski. J. Lumin. 2001, Vol. 94/95, p. 59]. An effective emission under direct excitation and phosphorescence in the red spectral range

(broad spectrum with λ max = 612 nm) was observed in microcrystalline (d 5 o * 1 ym) [Ping Zhang, Mingxia Xu,

Zhentai Theng, Lan Liu, Lingxia Li. J. Sol-Gel Sei. Techn. 2007, Vol. 43, pp. 59-64] and nanocrystalline

(d 50 * = 80-100 nm) [Ping Zhang, Mingxia Xu, Zhentai Theng, Bo Sun, Yanhui Zhang. Mat. Be. and Engineering ¬ ring B 2007, Vol 136, pp 159-164] Sr 3 Al 2 0. 6: Eu 2+, Dy 3+ detects powder. The PSL of this composition has not been reported in the literature.

Example of the preparation of a Si0 2 @Zn 2 Si0: Mn 2+ core-shell nanoparticle system. The synthesis of luminescent core-shell nanoparticles was carried out in a two-step process: coating of the silica cores and sintering of the coated nanoparticles. These were quasi monodisperse silica cores of different particle sizes (D = 75, 110, 140, 260 nm) according to a modified

Method according to Stoeber et al. (W. Stoeber, A. Fink, E. Bohn, J. Colloid Interface Sci., 1968, 26, 62; C. Gellermann, W. Storch, H. Wolter, J. Sol-Gel Sci.

Technol. 1997, 8, 173) by hydrolysis of TEOS

(Si (OEt) 4 in alcohol in the presence of water and

Ammonia produced. The particle size of the silica colloids was adjusted by concentration of the reactants and the temperature during particle growth. Isolation of the resulting silica particles was achieved by distilling off the solvent and washing the particles three times with ethanol. The resulting silica cores showed a spherical morphology and a narrow size distribution (polydispersity between 1 and 3%). In the first step, the cores were treated with Zn 2 Si0 4 : Mn 2+ precursors using a modified Pechini sol gel.

Process (see for example US 3,330,697) coated at room temperature. The doping concentration of Mn 2+ was varied between 1 mol% and 20 mol%, based on Zn 2+ in Zn 2 Si0 4 . The amount of starting material was calculated to give a shell thickness of 5 nm. The shell starting materials were dissolved in an aqueous-ethanol solution in the presence of nitric acid, citric acid chelating agent and polyethylene glycol (PEG) as the crosslinking agent. The network formation after chelation of

Zn 2+ and Mn 2+ ions resulted in a stabilization of the metal ions and a homogeneous distribution in the shell material on the surface of the silica core. The silica cores used ensured a spherical shape of the resulting core-shell

Nanoparticles and served as a silicate source for the resulting Zn 2 Si0 4 shell. In the final step, the nanoparticles were heated to a temperature between 800 ° C and 1100 ° C and held there for a short time to crystallize. Because of their specific surface area and strong interaction between the nanoparticles, they tend to coagulate and form aggregates during the final thermal treatment. To reduce particle agglomeration during annealing, pretreatment of the coated nanoparticles was accomplished by flash freezing followed by lyophilization. Lyophilization involves the sublimation of water under vacuum conditions from the frozen sample. This pretreatment leads to a loose storage of the nano- Particles side by side and prevents the melting of the particles during the temperature treatment. Dispersion tests were carried out to determine the amount of isolated particles as well as the fraction of non-redispersible aggregates. Despite the spray-drying of the particle samples, a fraction of non-redispersible aggregates was obtained, which were sorted out by selective sedimentation. Table 1 shows the degree of aggregation correlated with particle size. The amount of non-redispersible aggregates increases as the primary particle size decreases.

Figure imgf000031_0001

 (a) Sample designation is composed of the diameter of the silica core (determined by dynamic light scattering (DLS)) and the shell desired in the synthesis (b) Determined by DLS

To avoid aggregation, the sintering temperature is also of great importance. Observations on nanoparticles of the same size show that the amount of non-redispersible aggregates increases with increasing temperature. In the case of a nanoparticle with a core diameter of 75 nm, an increase in the aggregate fraction of up to 90% by weight was observed at temperatures above 1100 ° C. These results demonstrate the importance of choosing the synthesis parameters in accordance with the Particle size and the importance of further optimizing the manufacturing process for the production of aggregate-free nanoparticles. FIG. 1 shows a TE absorption of Si0 2 cores (d =

140 nm, Fig. 1a) and core-shell nanoparticles, which were sintered at 900 ° C (Fig lb:

Si0 2 @Zn 2 Si0 4 : Mn 2+ core-shell particles with a Mn 2+ doping concentration of 5 mol%). After coating the silica cores with a Zn 2 Si0 4 : Mn 2 layer, the resulting core-shell nanoparticles still retain their spherical shape. However, no increase in the diameter of the nanoparticles was found for core-shell nanoparticles compared to pure silica cores. This is on the

Shrinkage of the silica core during sintering at high temperatures due. Because of the different electron permeability of the core and shell material, the core-shell structure of the Si0 2 @Zn 2 Si0 4 : Mn 2+ nanoparticle can be clearly recognized

(see Figure lb).

The enveloping Zn 2 Si0 layer is continuous, but not of constant thickness. This can be explained by the fact that the Si0 2 core is responsible not only as a matrix for the morphological properties, such as the spherical shape, but also as a source for the formation of the silicate during the growth of the ZnSiO: Mn 2+ layer is. Obviously, the ZnSi0 4 : Mn 2+ shell does not form uniformly on the surface of the silica cores. Structural properties of Si0 2 @Zn 2 Si0 4 : Mn 2+ core-shell nanoparticles

The sintering temperature plays an important role, not only in the formation of aggregates during the

Particle preparation, but also with respect to the structural properties of the Mn 2+ -doped zinc orthosilicate (Takesue, K. Shimoyama, S. Murakami, Y. Hakuta, H. Hayashi, RL Smith Jr., J. Supercrit. 2007, 43, 214). To study the effects of temperature on the formation of the crystalline phase of the nanoparticle shell, samples were sintered at various temperatures between 800 and 1100 ° C and analyzed by XRD. Figure 2 shows the change in the crystalline phase obtained as a function of the sintering temperature. FIG. 2 shows XRD diffraction patterns of the Si0 2 @Zn 2 Si0 4 : Mn 2+ core-shell nanoparticles which were annealed at different temperatures (d = 75 nm, doping concentration of Mn 2+ : 5 mol%). The bottom line indicates the line positions of the a-Zn 2 Si0 4 lattice [PDF 37-1485; Circles] and the ZnO lattice [PDF 36-1451; Asterisk].

All samples show the formation of a crystalline layer around the amorphous silica core. The XRD analysis shows, however, that at 800 ° C mainly a ZnO phase is formed. In the case of Si0 2 @Zn 2 Si0 4 : n + nanoparticle samples, which were sintered at 900 ° C, the formation of two phases was detected: ZnO and α-Zn 2 Si0 4 . The intensities of the reflections of the willemite increase with increasing firing temperature, and a predominant oi-Zn 2 Si0 4 phase is observed in samples which are heat treated at 1100 ° C. In addition, no influence of the Mn 2+ concentration on the formation of the crystalline shell structure was observed. On the one hand, these results show the Importance of temperature treatment for Schalenbil ¬ tion, which consists only of a pure zinc-silicate phase. On the other hand, these results can be used to understand the phase-forming process during shell growth. The mechanisms of the crystalline shell phase formation can be summarized as shown in FIG. According to the formation of the core-shell-structured Si0 2 @Zn 2 Si0 4 : Mn 2+ nanoparticles proposed in FIG. 3, in a first step Zn 2+ and Mn 2+ are produced by

Chelatisierung and polymerization are stabilized, homogeneously distributed in the starting solution and adsorbed on the colloidal silica particles to form a gel layer (1). Heating of the coated particles at 800 ° C causes the formation of a Mn + - doped ZnO shell (2). The Zn 2 Si0 4 phase begins to form with tempering at 900 ° C (3). Further elevation of the temperature to 1100 ° C induces the formation of pure Mn 2+ -doped a-Zn 2 Si0 4

(Willemite) (4).

In the first step of the Pechini process, the starting materials are dissolved in the reaction solution. Zn 2+ and Mn 2+ ions are stabilized by citric acid (cholate formation) and polymerized by reactions of the remaining carboxylic acid groups with PEG (polyesterification). This ensures a homogeneous distribution of the metal cations in the polymeric network and the subsequent adsorption of metal ions on the silica core surface (see step (1) in FIG. 3). During the temperature treatment, the organic components decompose; the reaction takes place on the interface between Si0 2 and Zn 2+ and Mn 2+ . A temperature of about 800 ° C is needed to form a zinc oxide phase (see step (2) in Figure 3). Another increase in temperature leads to the transformation of ZnO into the Zn 2 Si0 4 phase (see step (3) in FIG. 3). At temperatures Zvi ¬ rule 900 and 1000 ° C coexist ZnO and Zn 2 Si0 4 crystal in a mixed system. The transformation of the ZnO phase into zinc silicate proceeds through further

Diffusion of ZnO into the silica matrix continues (C. Xu, J. Chun, K. Roh, D. E. Kim, Nanotechnology 2005, 16, 2808). The reaction along the interface between ZnO seed crystals and the silica surface can be represented by the following equation (1):

2ZnO + Si0 2 -> Zn 2 Si0 4 (1)

The XRD results prove that the arrangement of the zinc silicate phase progresses by forming the ZnO phase formed at the beginning of the sintering process (Figure 2). The formation of the pure Zn 2 Si0 4 - shell takes place at temperatures of 1100 ° C (see step (4) in Figure 3).

Optical properties of SiQ 2 @Zn 2 SiQ 4 : Mn 2 core-shell nanoparticles

The UV-excited photoluminescence spectra of the particles are dominated by a strong green emission band with a maximum around 525 nm (FIG. 4). FIG. 4 shows the photoluminescence spectra of FIG

Si0 2 @Zn 2 Si0 4 : Mn 2+ nanoparticles annealed at 1100 ° C (1), 1000 ° C (2), and 900 ° C (3). The measurements were carried out at 300 K with an excitation at 260 nm. The doping concentrations are 5 mol% (1, 2) and 1 mol% (3). This corresponds to the Ti ( 4 G) - ^ emission of the Mn 2+ ions in a-Zn 2 Si0 4 , which are substituted in the tetragonal Zn atoms. Sites are confirmed, which confirms the formation of the a-Willemite structure (ALN Stevels, AT Vink, J. Lumin 1974, 8, 443). A slight shift of the maximum wavelength with increasing Mn 2+ concentration is related to the relative population of the two non-equivalent Zn sites. The decrease in luminescence in lightly doped samples is exponential, with a lifetime of approximately 20 ms, which is typical for forbidden dd junctions. FIG. 5 shows the photoluminescence decay of FIG

Si0 2 @Zn 2 Si0 4 : Mn 2+ nanoparticles doped with 1 mol% (1), 5 mol% (2) and 20 mol% (3) n 2+ in the case of pulsed excitation 260 nm, at room temperature. The emission maximum was detected at 525 nm. As shown in Figure 5, those doped with 1 mol%

Still samples an exponential drop. A slight non-exponential decay of the 5 mol% sample demonstrates concentration quenching according to Inoue et al. (Y. Inoue, T. Toyoda, J. orimoto, J. Mater, Sci., 2008, 43, 378) and Sohn et al. (K.-S.

Son, B. Cho, HD Park, Mater. Lett. 1999, 41, 303) quenching begins at 6 to 7 mol%; it is possible that the inhomogeneous distribution of Mn 2+ ions in the samples also leads to quenching at lower concentrations. A stronger quenching effect is observed for samples doped with a nominal 20 mol%.

The photoluminescence spectra as well as the decay curves are measured at 260 nm excitation, which leads to a transfer of the electrons from Mn 2+ ground state into the conduction band of Zn 2 Si0 4 and a subsequent recombination. It is also possible to excite the luminescence in band between 340 nm and 399 nm, which is the transition from the 6 Ai (S) ground state of Mn 2+ - Ions corresponding to 4 E ( 4 D) and 4 T 2 (D) excited states.

Surface modification of SiQ 2 @Zn 2 SiQ 4 : Mn 2+ core-shell nanoparticles

With regard to the use of Si0 2 @Zn 2 Si0 4 : Mn 2+ core-shell nanoparticles as luminescent markers in biological and medical diagnostic systems, further surface modification of zinc silicate-coated nanoparticles with amino and carboxyl functionalities has been proposed for further attachment of Biomolecules shown. Surface analogues of Zn 2 Si0 4 and Si0 2 demonstrate the possibility of transferring the functionalization methods for silica particles to the zinc silicate surfaces. The nanoparticles were modified by covalent attachment of the amino silane N- [3- (trimethoxysilyl) -propyl] diethylenetriamine (TRIAMO) via the silanization method (see also Van Blaaderen, A., Vrij, A., J. Colloid Interface Sci 1993, 156, 1 and Waddell, TG;

Leyden, DE; DeBello, MT, J. Am. Chem. Soc, 1981, 103, 5303). The success of the surface modification was determined by measurements of the ζ potential as a function of the pH (see FIG. 6). FIG. 6 shows the ζ potential of unmodified and functionalized Si0 2 @Zn 2 Si0 4 : Mn 2+ nanoparticles as a function of the pH before functionalization (1) and after surface modification with amine (2) and carboxyl - (3) functionalities. The diagram shows the shift of the electrical point after modification with amino and carboxyl functionalities.

This measurement clearly showed the change of the surface properties by the reaction with

TRIAMO. The isoelectric point (IEP), which in a The pH of 3.1 for the initial unmodified Si0 2 @Zn 2 SiO, j: Mn 2+ core-shell nanoparticles is close to the values for pure silica particles Schiestel, H. Brunner, GEM Tovar, J. Nanosci, Nanotechnol., 2004, 4,

504). The shift of the isoelectric point to pH 7 after amino functionalization showed the successful binding of the aminosilane to the surface of the nanoparticles. Succinic anhydride was used to introduce carboxyl groups to the particle surface in an analogous manner (X. Zhao, LR Hilalard, SJ Mechery, Y. Wang, RP Bagwe, S. Jin, W. Tan, Proc. Nat. Acad 2004, 101, 15027) the isoelectric point of 3.5, which was found for the carboxylic acid modified nanoparticles, suggests that the cyclic anhydride molecules had reacted with the amino groups via a ring-opening reaction to form an amide functionality, resulting in a Spacer extension and the introduction of carboxyl functionalities in place of the

Suggests amine on the surface of the nanoparticles. The terminal carboxyl groups, which are directed into the surrounding solution, stabilize the nanoparticles in an aqueous environment and allow immobilization on amine-containing biomolecules, such as proteins. Thus, surface-modified luminescent Si0 2 @Zn 2 SiO 4 : Mn 2+ core-shell nanoparticles can be used directly in a multiplicity of biological and medical diagnostic applications.

In accordance with the above, it is possible to redispersible core-shell-structured luminescent nanoparticles with particle sizes in a range of 10 and 290, preferably 75 and 260 nm successfully via a sol-gel process, which of a sintering step at high temperatures is carried out manufacture. The crystal structures of the shell and the photoluminescence intensity of the core-shell nanoparticles can be adjusted by selecting the sintering conditions and varying the concentration of the metal used for the doping, for example Mn 2+ . At temperatures above 800 ° C, preferred

900 ° C., the shell forms, which is preferably a-Zn 2 Si0 4 , which is characterized by a long lifetime of the emission of luminescence, for example Mn 2+ at a wavelength of 525 nm.

The successful additional functionalization of nanoparticle surfaces suggests that, in principle, conventional silanization methods can be used to modify Zn 2 Si0 4 : Mn 2+ -based nanoparticles. According to the present invention, nanoparticles of controlled

Particle size, morphology, crystal structure and optical properties are produced, as well as the aggregation of the nanoparticles and their agglomeration can be controlled. Moreover, the present invention offers considerable potential applications of the luminescent nanoparticles in various biotechnological applications.

example

Preparation of monodisperse silica cores: monodisperse silica cores were replaced by the modified silica cores

Stoeber method (W. Stoeber, A. Fink, E. Bohn, J.

Colloid Interface Be. 1968, 26, 62 and C.

 Gellermann, W. Storch, H. Wolter, J. Sol-Gel Sei.

Technol. 1997, 8, 173). In a typical synthesis, 225 g of TEOS were dissolved in 4.5 l of ethanol

Presence of 225 ml of ammonium hydroxide hydrolyzed. The resulting clear, colorless mixture was then aged at room temperature for 3 days. The isolation of the resulting silica cores was accomplished by distilling off the solvent and then washing three times with ethanol.

Preparation of Si0 2 @Zn 2 Si0 4 Core-Shell Nanoparticles: The surface coating with an Mn 2+ -doped zinc silicate layer was carried out by a modified Pechini process (DY Kong, M. Yu, CK

Lin, XM Liu, J. Lin, J. Fang, J. Electrochem. Soc. 2005, 152, H146). In a typical reaction, 31.2 g (142 mmol) Zn (0 2 C 2 H 4) · 2H 2 0 and 1.29 g (7.47 mmol) of Mn (C 2 H 4 0 2) 2 (doping concentration 5 mol%) in a solution of 1.07 1 ethanol and 133 ml

Water (ethanol / water = 8/1 vol / vol) dissolved. After adding 20 ml of nitric acid, the reaction mixture was sonicated to dissolve the starting materials. Subsequently, 62.6 g (298 mmol) of citric acid monohydrate were used as chelating agent.

Agent and 63.1 g (5.49 to 7.43 mmol) PEG ( w = 10,000) was added as a crosslinker. The reaction mixture was stirred and sonicated for 2 h. A dispersion of monodisperse silica cores was added to the above solution.

The resulting suspension was stirred for 3 h at room temperature. The reaction mixture was then centrifuged and the precipitate was freeze-dried. The lyophilized nanoparticle powder was heated to 100 ° C for 1 hour in an oven and sintered at the required temperatures (800 to 1100 ° C) at a heating rate of 200 K / h, keeping it at the sintering temperature for 15 minutes.

Surface modification: The following steps were carried out in an argon atmosphere. 5.73 ml am- monohydroxide and 44.6 μΐ (173 pmol) of TRIAMO were added to a dispersion of 1.00 g of the core-shell nanoparticles in ethanol prepared by a coating process mentioned above. The solution was stirred for 16 h at room temperature. The amino-functionalized nanoparticles were centrifuged off and washed three times with ethanol. To form the carboxyl functionalities on the nanoparticle surface, 100 mg of the amino-functionalized nanoparticles were transferred to THF (70 ml). 6 ml succinic anhydride solution in THF (2 mol / l) was added to the nanoparticle suspension with sonication. The suspension was stirred for 16 h at room temperature. The resulting carboxyl-modified nanoparticles were washed three times thoroughly in deionized water.

Application example:

In this case, Zn 2 Si0 4 : Mn 2+ (5 mol%) of sample PSL was measured.

The sample was irradiated with a xenon flash lamp through 260 nm interference filters for 1 minute.

Repetition rate 10 Hz, pulse energy 18 microjoules, pulse duration 4 microseconds, irradiated area approx.

1.5 cm 2 . Absorbed dose about 7 mJ / cm 2 .

For stimulation, a red LED with the wavelength 640 nm was used.

Power density approx. 2.5 mW / cm 2 . The picture also shows afterglow (phosphorescence). Even after a few minutes, if afterglow is already gone, you can measure PSL.

The measurement curve is shown in FIG. 7.

Claims

claims
Photo-stimulable nanoparticles, which can be converted into an electronically charged state by supplying energy and can be induced to emit electromagnetic radiation by means of stimulation by electromagnetic radiation.
Nanoparticle according to Claim 1, characterized in that the half-life ti2 of the spontaneous decay of the charged state is at least 1 s, preferably at least 1 min., Particularly preferably at least 30 min.
Nanoparticles according to one of the preceding claims, characterized in that the conversion into the electronically charged state by means of electromagnetic radiation, preferably by electromagnetic radiation having a wavelength between 100 to 1600 nm, in particular UV radiation, and / or by X-radiation and / or by electron beams he follows.
Nanoparticle according to one of the preceding claims, characterized in that the electromagnetic radiation used to stimulate the emission has a wavelength between 200 to 2000 nm, preferably between 400 to 1600 nm. Nanoparticle according to one of the preceding claims, characterized in that the wavelength of the emission between 200 to 4000 nm, preferably 400 to 1600 nm.
6. Nanoparticles according to one of the preceding claims, characterized in that the
 Particle size between 2 to 1000 nm.
Nanoparticle according to one of the preceding claims, characterized in that the nanoparticle is present as a core-shell nanoparticle
Photo-stimulable nanoparticles according to one of the preceding claims, comprising
a) an amorphous core of silica or of a compound selected from the group consisting of silica, silicates, vanadates, tungamates, phosphates, oxides, sulfides, sulfates, aluminates and / or halides, such as fluorobromides, of a first main group, B) a stimulable shell containing at least one compound selected from the group consisting of silica, silicates, vanadates, tungstates, phosphates, oxides, sulfides, sulfates, aluminates and / or halides, such as fluorobromides, a first main groups , Transition or lanthanide metal containing transition metal or lanthanide metal ions of at least one second, different from the first main group metal, transition metal or Lanthanidmetall a kind of transition metal or
 Lanthanide metal are doped,
 characterized by a diameter of
 Silica core between 10 and 290 nm, preferably between 10 and 260 nm, more preferably between 10 and 50 nm or 75 and 260 nm.
Nanoparticles according to claim 8, characterized in that the second, for doping verwen dete variety transition metal or
Lanthanide metal ion is selected from the group consisting of Pb 2+ , n 2+ , Cu + , Dy 3+ , Sm 3+ , Eu 2+ , Eu 3+ , Tb 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Gd 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ and / or combinations thereof.
Nanoparticles according to any one of claims 8 to 9, characterized in that the at least one compound selected from the group consisting of Sr (Ca) A1 2 0 4, MgSi0 3, ZnSi0 4, ZnMgSi 2 0 6, Sr 2 MgSi0 7, YV0 4 , GdV0 4 , NaGd (W0 4 ) 2 , CaW0 4 , Y 2 0 3 , LaP0 4 , ZnS, CaS, BaFBr and / or combinations thereof. 11. Nanoparticle according to one of the preceding claims, characterized by a surface functionalization, preferably an amino, carboxylate, carbonate, maleic, imine, imide, amide, aldehyde, thiol, isocyanate, isothiocyanate, Acylazide, hydroxyl, N-hydroxy succinimide ester, phosphate, phosphonic acid, sulfonic acid, sulfonyl chloride, epoxy, cc double bond-containing, such as (meth) acrylic acid or (meth) acrylate - or norbornyl Group-containing functionalization.
12. Nanoparticles according to one of the preceding claims, characterized in that the
 Particle surface with a shell of silica, polymer, alumina, titanium dioxide, zinc oxide, zirconia or polyethylene glycol is surrounded.
13. Nanoparticle according to one of the preceding claims, characterized in that the surface of the PLS particle is chemically modified and / or has covalently or non-covalently bound compound molecules and / or reactive groups.
1 . Nanoparticles according to one of the preceding claims, characterized in that one or more chain-like molecules having a polarity or charge opposite to the surface of the nanoparticles are connected non-covalently to the surface of the particles as the connecting molecule.
15. Nanoparticles according to one of the preceding claims, characterized in that the chain-like molecules are anionic, cationic or zwitterionic detergents, acidic or basic proteins, polyamides or polysulfone or polycarboxylic acids.
16. Nanoparticles according to one of the preceding claims, characterized in that the surface and / or with the surface of the nano Particle-linked compound molecules reactive neutral, charged or partially charged groups, such as amino groups, carboxylic acid groups, thiols, thioethers, disulfides, imidazoles,
Guanidines, hydroxyl groups, indoles, vicinal diols, aldehydes, alpha-haloacetyl groups, N-maleimides, mercury organyls, aryl halides, acid anhydrides, isocyanates, isothiocyanates, sulfonic acid halides, imido esters, diazoacetates, diazonium salts, 1,2-diketones, alpha-beta-unsaturated carbonyl compounds, Azolide, silanes, phosphonic acids, phosphoric acid esters or derivatives of said groups wear, said reactive groups allow chemical bonding with other compound molecules or affinity molecules.
Nanoparticles according to one of the preceding claims, characterized in that they molecules with one or more affinity molecules or more affinity molecules coupled together, wherein the affinity molecules on the one hand bind to the particle surface and on the other hand can bind to a biological or other organic substance are equipped.
Nanoparticles according to one of the preceding claims, characterized in that the Affi nitätsmoleküle monoclonal or polyclonal antibodies, proteins, peptides, oligonucleotides, plasmids, nucleic acid molecules, oligo- or polysaccharides, haptens, such as biotin or
Digoxin, or a low molecular weight synthetic or natural antigen. Nanoparticles according to any one of the preceding ¬ claims, characterized in that the Affi is nitätsmolekül coupled by reactive groups on the Affini tätsmolekül and on the simple detection probe covalently or non-covalently to the particle g.
Nanoparticles according to any one of the preceding claims, characterized in that the reac ¬ tive groups on the surface of the affinity molecule amino groups, carboxylic acid groups, thiols, thioethers, disulfides, imidazoles, guanidine dine, hydroxyl groups, indoles, vicinal diols, aldehydes, alpha-haloacetyl , N-alimides, mercury organyls, aryl halides, acid anhydrides, isocyanates, isothiocyanates, sulfonic acid halides, imido esters, diazoacetates, diazonium salts, 1, 2-diketones, alpha-beta-unsaturated carbonyl compounds or azolides.
Nanoparticles according to one of the preceding claims, characterized in that a covalent or non-covalent self-assembled compound exists between the PSL particle and the affinity molecule.
Photo-stimulable nanoparticle system containing nanoparticles according to one of the preceding claims with a preferred polydispersity of the nanoparticles between 0.1 and 10%, preferably between 1 and 3%. Photo-stimulable nanoparticle system according to the preceding claim in the form of a solution, a dispersion or a suspension.
Photo-stimulable nanoparticle system according to one of the two preceding claims, containing further additives, in particular
Stabilizers.
A process for the preparation of a photo-stimulable nanoparticle system according to one of the two preceding claims, wherein the amorphous core particles of silica or of a compound selected from the group consisting of silica, silicates, vanadates, tungstates, phosphates, oxides, sulfides, sulfates, aluminates and / or halides, such as Fluorobromides, a first main group, transition or lanthanide metal, with a mean diameter between 10 and 290 nm by wetting with an aqueous solution containing
a) at least one sort of ions of a first
 B) at least one type of ion of a second, of the first different transition metal or lanthanide metal and
c) in the event that the shell is vanadate,
olframates, phosphates, sulfides, sulfates, aluminates and / or halides should contain vanadate, olframat, phosphate, sulfide and / or halide ions, in particular fluoride and bromide ions, coated and the coated core particles are then tempered.
Method according to the preceding claim, characterized in that the aqueous solution additionally
a) an organic carboxylic acid having at least two acid functionalities, preferably citric acid, and / or
b) an alcohol having at least two alcohol functionalities, preferably polyethylene glycol and / or polypropylene glycol
contains.
Use of a nanoparticle system according to one of claims 22 to 23 as a diagnostic agent
and / or as markers, in particular for biological or medical uses; as an optically detectable diffusion probe; in
Security systems; as a substrate for security systems and / or as a marker for the detection of originals and / or plagiarism and / or as a contrast agent for biomedical examinations and / or as a means for forensic investigations, wherein preferably the nanoparticle system with light of a wavelength between 100 and 800 nm, with X-ray - And / or electron beams is converted into an electronically charged state, and is excited by means of a light pulse having a wavelength between 400 and 1600 nm for the stimulated emission of photons having a wavelength between 400 and 1500 nm.
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