Upconversion fluorescent nano-structured material and uses thereof

Abstract

Upconversion fluorescent nano-structured material(s) comprising at least one compound of formula (M 1 ) j (M 2 ) k X n :(M 3 ) q and at least one polymer, wherein: each X is the same or different and is selected from the group consisting of: halogen, O, S, Se, Te, N, P and As; each M 1 , if present, is the same or different and is selected from the group consisting of: Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, O and NH 4 ; each M 2 is the same or different and is a metal ion; each M 3 , independently, is the same or different and is selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; j is 0≦j≦10; k is 1≦k≦10; n is 1≦n≦10; and q is 1≦q≦10. In particular, the polymer is wherein the polymer soluble in polar solvents.

1. An upconversion fluorescent nano-structured material comprising at least one compound of formula (M 1 ) j (M 2 ) k X n :(M 3 ) q  and at least one polymer, the polymer having a concentration of 5-25 weight %, wherein
 each X is the same or different and is selected from the group consisting of: halogen, O, S, Se, Te, N, P and As; 
 each M 1 , if present, is the same or different and is selected from the group consisting of: Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, O and NH 4 ; 
 
       each M 2  is the same or different and is a metal ion;
 each M 3 , independently, is the same or different and is selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; 
 
       j is 0≦j≦10; k is 1≦k≦10; n in 1≦n≦10; and q is 0≦q≦10,
 and wherein the polymer is on the nano-structured material. 
 
     
     
       2. The upconversion fluorescent nano-structured material according to  claim 1 , wherein q is 2. 
     
     
       3. The upconversion fluorescent nano-structured material according to  claim 1 , wherein M 2  is selected from the group consisting of: transition metal ions, inner transition metal ions, and Group I to Group VI metal ions. 
     
     
       4. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the polymer has an average molecular weight of about 10-40 kDa. 
     
     
       5. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the polymer is selected from the group consisting of: polyethylenimine (PEI), Poly-l-lysine (PLL), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), poly(ethylene glycol) (PEG), poly(4 vinylpyridine) (P4VP), oleic acid, stearic acid, chitosan and mixtures thereof. 
     
     
       6. The upconversion fluorescent nano-structured material according to preceding  claim 1 , wherein each M 3  is different and is selected from the group consisting of: Yb, Er, Tm and Ho. 
     
     
       7. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material is selected from the group consisting of: PEI/NaYF 4 ; PEI/NaYF 4 :Yb,Er; PEI/NaYF 4 :Yb,Tm; PEI/NaYF 4 :Yb,Ho; PVP/NaYF 4 ; PVP/NaYF 4 :Yb,Er; PVP/NaYF 4 :Yb,Tm; PVP/NaYF 4 :Yb,Ho and a combination thereof. 
     
     
       8. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material has a crystal structure selected from the group consisting of: hexagonal, cubic, tetragonal, rhombohedral, orthorhombic, monoclinic, triclinic and a combination thereof. 
     
     
       9. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material comprises at least one dimension of size ≦100 nm. 
     
     
       10. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material is in the form of: nanoparticle(s), nanofilm or monolith. 
     
     
       11. The upconversion fluorescent nano-structured material according to  claim 1 , further comprising at least one layer of silica which is disposed about the nano-structured material and which modifies the surface of the nano-structured material. 
     
     
       12. The upconversion fluorescent nano-structured material according to  claim 11 , wherein the at least one layer of silica is doped with a fluorescent dye or quantum dot. 
     
     
       13. The upconversion fluorescent nano-structured material according to any preceding  claim 1 , further comprising at least one photosensitizer which is disposed about the nano-structured material. 
     
     
       14. The upconversion fluorescent nano-structured material according to  claim 1 , further comprising at least one biomolecule attached to the nano-structured material. 
     
     
       15. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material is soluble in water and/or polar solvents. 
     
     
       16. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material is a NIR-to-visible upconversion fluorescent nanoparticle. 
     
     
       17. An article of manufacture comprising the upconversion fluorescent nano-structured material according to  claim 1 . 
     
     
       18. The article of manufacture according to  claim 17 , wherein the article of manufacture is at least one of the following: a display device, a solar cell, an optical data storage, a bio-probe, a carrier for drug delivery, a lamp, a LED, a LCD, a wear resistance, a laser, optical amplifier, and/or a device for bio-imaging. 
     
     
       19. The article of manufacture according to  claim 17 , wherein the article of manufacture is a bio-imaging and/or bio-detection apparatus comprising:
 at least one upconversion fluorescent nano-structured material according to  claim 1 ; 
 at least one biomolecule; 
 at least one source of excitation; and 
 at least one means for delivery of the source of excitation to the apparatus. 
 
     
     
       20. The apparatus article of manufacture according to  claim 19 , wherein the source of excitation is NIR. 
     
     
       21. The apparatus article of manufacture according to  claim 20 , wherein the NIR is at 980 nm. 
     
     
       22. The article of manufacture according to  claim 19 , wherein the means for delivery of the source of excitation to the apparatus is selected from the group consisting of: optical fibres, LED, endoscopes, external light and external laser. 
     
     
       23. A method for photodynamic therapy, non-invasive bio-imaging and/or non-invasive bio-detection, the method comprising the step of administering to a subject the nano-structured material according to  claim 1 . 
     
     
       24. A method of preparing at least one upconversion fluorescent nano-structured material as defined in  claim 1 , comprising:
 a. mixing ions of at least one M 3  and at least one M 2  to obtain a mixture; 
 b. adding at least one polymer to the mixture; and 
 c. adding ions of at least one X. 
 
     
     
       25. The method according to  claim 24 , further comprising adding the polymer in the presence of ions of at least one M1. 
     
     
       26. The upconversion fluorescent nano-structured material according to  claim 1 , wherein the nano-structured material is biocompatible.