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    • 专利摘要:
    Luminescent materials upconversion and method of preparation thereof. The present invention relates to nanoparticles of formula mlnf4: re3, where m is an alkali metal, ln is a lanthanide element or an analogue thereof and re <sup > 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise organic ligands bonded to their surface by covalent bonds. The invention furthermore relates to a method of preparing the upconversion luminescent nanoparticles of the invention, to the use of the upconversion luminescent nanoparticles of the invention as fluorescent or photosensitizing markers and to a luminescent composite comprising the luminescent nanoparticles of upconversion of the invention. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2648639A1
    申请号:ES201630886
    申请日:2016-06-30
    公开日:2018-01-04
    发明作者:Julia PÉREZ PRIETO；María GONZÁLEZ BÉJAR；Néstor Luis ESTÉBANEZ BLOEM；José Francisco Fernández Lozano；Esther ENRÍQUEZ PÉREZ；Ángel Miguel LÓPEZ BUENDÍA；María Del Mar URQUIOLA CASAS
    申请人:Innceinnmat SL；INNCEINNMAT S L；Consejo Superior de Investigaciones Cientificas CSIC；Universitat de Valencia；
    IPC主号:
    专利说明:

    Luminescent upconversion materials and their preparation method
    5 Field of the invention
    The present invention is related to the area of upconversion luminescent materials. More specifically, the present invention is related to upconversion nanoparticles and luminescent composites and methods for
    10 preparation thereof.
    Background of the invention
    The upconversion processes consist of the emission of photons at high energy in the
    15 ultraviolet-visible-near-infrared interval after sequential absorptions of lower energy photons, usually in the near infrared. At present, the development of nanoparticles constituted by the combination of a suitable crystalline matrix and certain trivalent lanthanide ions (Ln3 +), which are capable of producing efficient emission by upconversion (“Lantanide-upconversion nanoparticles” Ln-UCNPs), has
    20 acquired great relevance in the field of nanophotonics, such as NaYF4 doped with rare earths such as Er3 +, Yb3 + and / or Tm3 +. This is due to the long half-life of the photoluminescence of the Ln3 + (from µs to several ms), and to the low optical power density required by the excitation of the Ln-UCNPs, which makes it possible to use lasers diode continuously as a source of excitation (much more
    25 cheaper than the pulsed lasers that are normally required). In addition, Ln-UCNPs can emit at different wavelengths through the selection or combination of Ln3 + ions, have low toxicity and extraordinary photostability. These formulation materials type NaYF4: Yb, Er (Tm) have been known since the 1970s (Menyuk N. et al .; Appl. Phys. Lett., 1972, 21, 159; Sommerdijk J.L. and Bril A.,
    30 Philips Tech. Rev. 1974, 34, 1) due to its upconversion effect, and were subsequently obtained in nanometric size (Zeng J. H. et al .; Adv. Mater. 2005, 17, 2119).
    All these advantages of Ln-UCNPs allow a wide variety of photonic applications as luminescent markers acting as safety elements (WO
    35 2014/090867 A2, Chen G. et al .; Chem. Soc. Rev., 2015, 44, 1680-1713) or in imaging techniques in diagnosis and biomedicine (US 2009/0081461 A1), in which the use


    near-infrared excitation allows greater depth of penetration into biological tissues, with minimal damage to living organisms. They are also applied in the manufacture of screens and luminous devices, and in white light generation technology, for which the incorporation of Ln-UCNPs in hybrid composite materials is required, by dispersion or infiltration in vitreous or polymeric materials, and by deposit as thin sheets on crystalline substrates, materials all transparent in the near infrared. The generation of white light by balance of the upconversion emissions of the Ln-UCNPs is an alternative to other white light systems such as LEDs.
    The research and development of previous photonic applications have been possible thanks to the development of a wide variety of chemical pathways for the preparation of Ln-UCNPs, including mainly co-precipitation (Wang LY et al .; Angew. Chem., Int. Ed . 2005, 44 (37), 6054–6057), thermal decomposition (Q. Li and Y. Zhang, Nanotechnology 2008, 19, 345606), solvotermal synthesis (Rhee HW et al .; J. Am. Chem. Soc. 2008 , 130 (3), 784-785), combustion synthesis (Liu YS et al .; Chem. Soc. Rev. 2013, 42 (16), 6924-6958) and sol-gel synthesis (Patra A. et al. ; J. Phys. Chem. B 2002, 106 (8), 1909-1912).
    In all these synthetic routes, the Ln-UCNPs obtained are passivated with organic ligands anchored to the surface of the nanoparticles by noncovalent interactions and using anionic groups or with free electron pairs, such as carboxylate, phosphate, thiolate or amines groups. International application WO 2012/091778 A2 describes Ln-UCNPs of NaYF4: Yb, Er, Gd2O2S: Yb, Er, Y2O3: Yb, Er, CeO2 or NaGdF4: Tb, all passivated with oleate. US application US 2010/0261263 A1 describes Ln-UCNPs with core / shell structure comprising a core of Y2O3: Ln with NaYF4 sheath and passivated with polyethylene glycol or polyethyleneimine. The ligands are essential to control the size and shape of the Ln-UCNPs during their synthesis process in solution, as well as to prevent the collapse of the nanoparticles and, as a consequence, their precipitation.
    The Ln-UCNPs obtained by these methods are generally hydrophobic, this being a disadvantage for various applications for which it is necessary that the Ln-UCNPs be dispersible in aqueous media, for example for application in biological samples. This drawback is usually solved in the state of the art by exchange of the ligand or passivated with macromolecules as polymers (Muhr V.


    et al .; Acc. Chem. Res., 2014, 47 (12), 3481–3493) or oxidation of the ligand (Naccache R. et al .; Chem. Mater., 2009, 21 (4), 717–723) in order to confer hydrophilicity to the Ln-UCNPs.
    However, the passivation with organic ligands of the Ln-UCNPs described in the state of
    5 The technique has low stability in acidic media because the ligands usedthey become uncoordinated from the surface of the nanoparticle at acidic pH (Liras M. et al .; Chem.Mater. 2014, 26, 4014-4022). In fact, it is usual to remove carboxylate ligandsanchored to Ln-UCNPs by protonation at pH ca. 4 (Bogdan N. et al .; Nano Lett.,2011, 11, 835-840). This low stability of the organic passivate against acidic pHs means
    A disadvantage for the use of this type of nanoparticles in numerous applications that require an acid medium, such as the synthesis of ceramic composite materials by the sol-gel technique such as those required in the present invention.
    Therefore, despite the great variety of Ln-UCNPs and their synthesis routes
    15 described in the state of the art, there is still a need to obtain new Ln-UCNPs stable in acidic media and with high upconversion efficiency. These new Ln-UCNPs must also be applicable as particulate or sheet materials maintaining their transparency and preferably with stability and hardness of ceramic type. Although the preparation of ceramic coatings has been described by the sol-gel technique, as per
    20 example in WO 2012/113953 A1, there is still a need in the state of the art for ceramic coatings comprising Ln-UCNPs with high luminescent efficiency.
    Brief Description of the Invention
    The authors of the present invention have developed nanoparticles with luminescent upconversion properties, stable in extremely acidic media as a result of the strong binding of organic ligands to the surface of the nanoparticles. In addition, the nanoparticles of the invention are soluble in aqueous medium and can be
    30 conjugated to other molecules, and therefore, change their interaction with the medium (solubility) or incorporate functional molecules.
    Therefore, a first aspect of the invention relates to nanoparticles of formulaMLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analogue of
    35 itself and RE + 3 is a rare earth ion or combinations thereof; characterized


    because said nanoparticles comprise organic ligands attached to their surface by covalent bonds.
    The nanoparticles of the invention have luminescent upconversion properties and are synthesized from naked precursor nanoparticles (UCNPnaked), characterized in that they comprise –O, -OH or –HOH groups on their surface that derive from the water molecules present in the medium of synthesis The UCNPnaked are previously obtained by, for example, treatment in acid medium of passivated UCNPs with oleate or other carboxylate ligands. The surface functionality of the UCNPnaked (-O, -OH or -HOH groups) is therefore used to obtain the nanoparticles of the invention (UCNP @ ligand, where "ligand" refers to an organic compound bound by a stable covalent bond to the surface of the nanoparticles).
    Therefore, another aspect of the present invention provides a method of preparing luminescent upconversion nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise organic ligands attached to their surface by covalent bonds, comprising the steps of:
    a) add to a polar solvent precursor nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise groups -O, -OH, -HOH or combinations thereof on their surface;
    b) add an excess base on the mixture resulting from step (a); Y
    c) after removing the excess base of the mixture resulting from step (b), add a compound of formula X-CH2CO-Z where X is a halogen, Z is -H, -R, -COR, -OH, - OCOR, -NH2, -NHR, -NR2, -NHCOR, -SR or -SCOR, and R is a linear or branched alkyl chain.
    A further aspect of the invention relates to nanoparticles of formula MLnF4: RE + 3 where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise organic ligands attached to their surface by covalent bonds, obtainable by the method of preparation as defined above.


    Another additional aspect of the present invention relates to the use of upconversion luminescent nanoparticles as defined above as fluorescent markers or photosensitizers.
    The present invention further provides a luminescent composite material comprising the luminescent upconversion nanoparticles as defined above. The combination of both components (matrix and nanoparticles) leads to an enhancement of the luminescent properties of upconversion and stability of the
    10 nanoparticles, and provides a composite material with high luminescent up-conversion performance.
    Therefore, another aspect of the present invention relates to a luminescent composite material comprising the luminescent upconversion nanoparticles as
    15 defined above.
    A further aspect of the present invention relates to the use of the luminescent composite material as defined above as a fluorescent or photosensitizer marker.
    Finally, another additional aspect of the present invention relates to the use of the luminescent composite material as defined above in the sectors of paper, plastic, packaging, textile, automobile, paints, biological, medical-pharmaceutical, document security, tracers, pigments. ceramic, optoelectronic or photovoltaic.
    25 Figures
    Figure 1: Comparison of FTIR spectra for UCNP @ ligand2-chloroacetamide at different pHs; where UCNP is NaYF4: Yb, Er.
    Figure 2: Comparison of emission spectra for UCNP @ ligand2-chloroacetamide at different pHs; where UCNP is NaYF4: Yb, Er where a) pH is 7.53 (control); b) pH is 2.00; c) pH is 2.00 after 2 hours; and d) pH is 7.53 after 48 hours.
    Figure 3: XPS C1s spectrum for 2-chloroacetamide (above) and for UCNP @ ligand235 chloroacetamide (below); where UCNP is NaYF4: Yb, Er.


    Figure 4: XPS N1s spectrum for 2-chloroacetamide (left) and for UCNP @ ligand2
    chloroacetamide (below); where UCNP is NaYF4: Yb, Er.
    Figure 5: XPS C1s spectrum for 2-chloroacetic acid (above) and for UCNP @ ligand2-chloroacetic acid5 (below); where UCNP is NaYF4: Yb, Er.
    Figure 6: XPS O1s spectrum for 2-chloroacetic acid (above) and for UCNP @ chloroacetic ligand (below); where UCNP is NaYF4: Yb, Er.
    Figure 7: Luminescence of the composite material comprising UCNP @ ligand2-chloroacetamide; where UCNP is NaYF4: Yb, Er, encapsulated by sol-gel procedure.
    Detailed description of the invention
    The main object of the present invention is to provide luminescent upconversion nanoparticles, more specifically nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is an ion of rare earths or combinations thereof; characterized in that said nanoparticles comprise organic ligands attached to their surface by covalent bonds, thus
    20 as ceramic composite materials of synergistic properties containing said nanoparticles.
    Upconversion processes consist of the emission of high-energy photons in the near-ultraviolet-visible-infrared range after sequential photon absorptions of
    25 less energy.
    Therefore, the nanoparticles of the invention have luminescent properties of upconversion with emission in the visible-ultraviolet-near-infrared range, after multiple excitations with lower energy photons, in particular in the near infrared.
    The nanoparticles of the invention may have a cubic, hexagonal, spherical, tetragonal, rhombohedral, monoclinic, triclinic structure or a combination thereof. The nanoparticles of the invention preferably have an average size of less than or equal to 500 nm, even more preferably between about 20 nm and about 500 nm.


    The nanoparticles of the invention have a matrix of formula MLnF4 doped with trivalent ions of rare earths RE3 + or combinations thereof and where M is an alkali metal and Ln is a lanthanide element or an analog thereof.
    5 In a preferred embodiment, M is Na or Li. In another preferred embodiment, RE3 + is Yb3 +, Er3 +,Tm3 +, Gd3 + or mixtures combinations thereof.
    The term "lanthanide element" refers to an element that is part of period 6 of the periodic table and is selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , Yb and
    10 Lu, preferably Yb.
    The term "analog thereof" refers to an element located within group 3 of the periodic table and which is chemically similar to a lanthanide element. In a preferred embodiment, the analog element is Y.
    15 A non-limiting example of matrix is NaYF4 doped with Yb3 +, Er3 +, Tm3 +, Gd3 + or combinations thereof.
    In a particular embodiment, the nanoparticles of the invention have structure
    20 core / shell. The term "core / shell structure" refers to nanoparticles that comprise a core of an inner material and a shell of an outer material. The nanoparticles obtainable by the method of preparation as defined above with a core / shell structure may have the same or different chemical composition for the inner material of the core and for the outer material of the shell. An example no
    Limiting nanoparticles of the invention with core / shell structure is NaYF4: RE3 + / NaYF4: RE3 + or NaYF4: RE3 + / NaYF4.
    The nanoparticles of the invention further comprise organic ligands linked by covalent bonds to their surface which comprise a unit -CH2CO-. This unit
    Short allows the ligands to remain tightly bound to the surface of the nanoparticles of the invention even in extremely acidic media, unlike anchoring groups by coordination or ionic bonds described in the prior art, which are uncoordinated from the surface of the nanoparticles in acidic pH media.


    The term "covalent bond" refers to a bond that occurs between two atoms with an electronegativity difference between said atoms less than 1.7, and in which said atoms reach the stable octet, sharing electrons of the last level.
    Therefore, in a particular embodiment, the nanoparticles of the invention comprise organic ligands attached to their surface by covalent bonds resistant to strongly acidic pHs, preferably at pHs between about 1.0 and about 4.0.
    Another aspect of the present invention provides a method of preparing luminescent upconversion nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a ground ion rare or combinations thereof; characterized in that said nanoparticles comprise organic ligands attached to their surface by covalent bonds, comprising the steps of:
    a) add to a polar solvent precursor nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise groups -O, -OH, -HOH or combinations thereof on their surface;
    b) add an excess base on the mixture resulting from step (a); Y
    c) after removing the excess base of the mixture resulting from step (b), add a compound of formula X-CH2CO-Z where X is a halogen, Z is -H, -R, -COR, -OH, - OCOR, -NH2, -NHR, -NR2, -NHCOR, -SR or -SCOR, and R is a linear or branched alkyl chain.
    Therefore, the method of preparing the nanoparticles of the invention comprises a step (a) which involves adding to a polar solvent precursor nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or a analogue thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise groups -O, -OH, -HOH or combinations thereof on their surface.
    In a preferred embodiment, M is Na or Li. In another preferred embodiment, RE3 + is Yb3 +, Er3 +, Tm3 +, Gd3 + or mixtures combinations thereof. In a preferred embodiment, Ln is Y.


    A non-limiting example of the matrix of the nanoparticles of the invention is NaYF4 doped with Yb3 +, Er3 +, Tm3 +, Gd3 + or combinations thereof.
    5 Non-limiting examples of polar solvents suitable for step (a) of the method ofinvention are dimethylformamide (DMF), acetonitrile (ACN), tetrahydrofuran (THF) or mixturethereof.
    In another preferred embodiment, step (a) of the method of the invention takes place at a temperature from about 25 ° C to about 80 ° C.
    The method of preparing the nanoparticles of the invention further comprises a step (b) comprising adding an excess base on the mixture resulting from step (a), as defined above.
    Suitable bases for step (b) of the method of the invention are inorganic bases, such as MOH type bases where M is an alkali metal, such as NaOH, KOH, LiOH or mixture thereof.
    In a preferred embodiment the excess base of step (b) of the method of the invention is an inorganic base, even more preferably NaOH.
    In another preferred embodiment, the base of step (b) of the method of the invention is added in excess between 10% and 50% by weight.
    The method of the invention further comprises a step (c) consisting of removing the excess base of the mixture resulting from step (b), as defined above, adding an organic compound of formula X-CH2CO-Z where X is a halogen, Z is -H, -R, -COR, -OH, -OR, -OCOR, -NH2, -NHR, -NR2, -NHCOR, -SR or -SCOR, and where R is a
    30 linear or branched alkyl chain.
    The compound of formula X-CH2CO-Z, which comprises a halogen directly bonded to the carbon in alpha to the carbonyl group (CO) and which is at an exact distance of two carbons (CH2CO) from Z, reacts with the reactive groups of the surface of the
    35 nanoparticles (–O, -OH or –HOH) forming a strong chemical bond (covalent bond)


    between them and allowing the ligand to remain tightly bound to the surface of the nanoparticles of the invention even in extremely acidic media.
    The group Z of the compound of formula X-CH2CO-Z brings functionality to the surface of the
    5 nanoparticles of the invention, which allows their conjugation with other moleculesfunctional and / or its interaction with the environment (solubility). In a preferred embodiment, Z is -H, -NH2 or -OCOR.
    The R group is a linear or branched alkyl chain. Non-limiting examples of R groups
    Suitable for step (c) of the method of the invention are -CH3, -CH2CH3, -CH2CH2CH (CH3) 2.
    Non-limiting examples of compounds of formula X-CH2CO-Z suitable for step (c) of the method of the invention are 2-chloroacetamide, 2-bromoacetamide, 2-chloroacetic acid,
    2-Bromoacetic acid, and 2-ethyl chloroacetate, preferably 2-chloroacetamide and 2-chloroacetic acid.
    In a particular embodiment, the method of preparing the nanoparticles as defined above comprises an additional step (d) comprising precipitating the
    20 nanoparticles obtained in step (c). The precipitation of the stage nanoparticles
    (d) of the method of the invention is preferably performed by centrifugation.
    In another even more particular embodiment, step (d) of the method of the invention further comprises washing and drying the precipitate.
    Therefore, the nanoparticles obtained through the method of the present invention are stable in extremely acidic media, because the reaction of the compound of formula X-CH2CO-Z with the reactive groups of the surface of the nanoparticles results in a covalent bond between them and that allows the ligand to remain
    30 strongly bound to the surface of the nanoparticles even in extremely acidic media.
    Therefore, a further aspect of the present invention relates to luminescent upconversion nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is
    35 a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise


    Organic ligands bound to their surface by covalent bonds, obtainable by the method of preparation as defined above.
    The nanoparticles obtainable by the method of preparation as defined
    5 previously have luminescent properties of upconversion with emission in thevisible range-ultraviolet-near infrared, after multiple excitations with smaller photonsenergy, particularly in the near infrared.
    The nanoparticles obtainable by the method of preparation as defined
    10 above may have a cubic, hexagonal, spherical, tetragonal, rhombohedral, monoclinic, triclinic structure or a combination thereof. The nanoparticles obtainable by the method of preparation as defined above preferably have an average size of less than or equal to 500 nm, even more preferably between about 20 nm and about 500 nm.
    The nanoparticles obtainable by the preparation method as defined above have a matrix of formula MLnF4 doped with trivalent ions of rare earths RE3 + or combinations thereof and where M is an alkali metal and Ln is a lanthanide element or an analogue thereof. .
    In a preferred embodiment, M is Na or Li. In another preferred embodiment, RE3 + is Yb3 +, Er3 +, Tm3 +, Gd3 + or combinations thereof. In a preferred embodiment, Ln is Y.
    A non-limiting example of the matrix of the nanoparticles of the invention is NaYF4 doped with Yb3 +, Er3 +, Tm3 +, Gd3 + or combinations thereof.
    In a particular embodiment, the nanoparticles obtainable by the method of preparation as defined above have a core / shell structure. The term "core / shell structure" refers to nanoparticles that comprise a core of a
    30 inner material and a shell of an outer material. The nanoparticles obtainable by the method of preparation as defined above with a core / shell structure may have the same or different chemical composition for the inner material of the core and for the outer material of the shell. A non-limiting example of nanoparticles obtainable by the preparation method as defined above.
    35 with core / shell structure is NaYF4: RE3 + / NaYF4 or NaYF4: RE3 + / NaYF4: RE3 +.


    The nanoparticles obtainable by the method of preparation as defined above are characterized in that they further comprise organic ligands covalently bonded to their surface which comprise a unit -CH2CO-. This short unit allows ligands to remain tightly bound, even in media.
    5 extremely acid-to the surface of the nanoparticles obtainable by the methodof preparation as defined above.
    Therefore, in a particular embodiment, the nanoparticles obtainable by the method of preparation as defined above are characterized in that they comprise
    10 organic ligands bound to their surface by covalent bonds resistant to strongly acidic pHs, preferably at pHs between about 1.0 and about 4.0.
    In addition, the nanoparticles of the present invention are stable both dispersed in aqueous or organic media, integrated in a masterbatch material or in powder form.
    15 fine, providing versatility to the dosing and storage thereof.
    Additionally, the nanoparticles of the present invention possess low toxicity and can be conjugated with bio-compatible molecules, which makes them compatible with applications such as fluorescent marker or photosensitizers, for example, of tumors, in the sector
    20 biological or medical-pharmaceutical.
    Therefore, another aspect of the present invention relates to the use of upconversion luminescent nanoparticles as defined above as fluorescent markers or photosensitizers, preferably in the biological or medical sector
    25 pharmacist
    The present invention further provides a luminescent composite material comprising the luminescent upconversion nanoparticles as defined above.
    In a preferred embodiment, the luminescent composite material as defined above is transparent.
    The term "transparent" refers to a material that easily lets light through the visible range.


    The term "composite material" refers to combinations of at least two types of materials to achieve the combination of properties that cannot be obtained in the original materials. These composite materials have a continuous and responsible matrix for physical and chemical properties, and a discrete load.
    In the composite material of the present invention, and as mentioned above, the combination of both materials (matrix and nanoparticles) results in a synergy effect since it enhances the luminescent upconversion and stability properties of the nanoparticles, and provides a composite material with high luminescent upconversion performance.
    In a particular embodiment, the luminescent upconversion nanoparticles comprised in the composite material of the present invention have an emitting capacity of more than 100 times with respect to the original upconversion luminescent nanoparticles, in an even more preferred embodiment of more than 600 times.
    In another particular embodiment, the luminescent composite material of the present invention is a ceramic composite. Said material comprises the nanoparticles as defined above encapsulated in a ceramic matrix.
    In a preferred embodiment, the luminescent composite material of the present invention is a ceramic composite material obtainable by a sol-gel synthesis process. By "sol-gel synthesis process" is understood those chemical routes widely known in the field of the art of the present invention and which comprise the synthesis of a colloidal suspension of solid particles in a liquid (called the sun) and hydrolysis and condensation of said sun to form a solid material filled with solvent (gel).
    In another preferred embodiment, the sol-gel synthesis process comprising the following steps:
    i) dispersion of the luminescent upconversion nanoparticles as defined above in a polar solvent comprising a metal alkoxide precursor, a dispersing agent and a surfactant;
    ii) adding water to the dispersion of step (i) to give rise to a hydrolysis reaction and formation of a sun; iii) condensation of the sun from step (ii) resulting in the formation of a gel; 14


    iv) aging and drying of the gel obtained in step (iii) to give rise to a ceramic luminescent composite; and v) densification of the composite material resulting from step (iv) by heat treatment.
    In step (i) of the sol-gel synthesis process of the present invention, the dispersion of the luminescent upconversion nanoparticles of the invention is dispersed in a polar solvent comprising a metal alkoxide precursor, a dispersing agent and a surface active agent, and optionally, a drying retarding agent.
    In the context of the present invention, the term "dispersing agent" refers to an additive that keeps the dispersion of step (i) of the sol-gel synthesis process of the invention stable. Non-limiting examples of dispersing agents suitable for the sol-gel synthesis process of the present invention are polyacrylates such as polyacrylic acid.
    In the context of the present invention, the term "surfactant" refers to an additive that modifies the contact surface between two phases and favors the wetting of the nanoparticles. The surfactant also includes a film forming or leveling agent such as a polyether modified polydimethylsiloxane.
    The dispersion of step (i) is obtained using high speed shear processes. Non-limiting examples of high speed shear dispersion suitable for step (i) of the sol-gel synthesis process of the present invention are Cowless type dispersion, dispersion using rotor-stator systems or systems such as attrition milling with
    25 microballs The means used must be effective in favoring the nanoparticles to be dispersed in the medium and if there are agglomerates, they must be within a size smaller than 200 nm.
    In a preferred embodiment, the polar solvent is an alcohol or mixture of alcohols, preferably a primary alcohol or mixture of primary alcohols.
    In another preferred embodiment, the luminescent stage upconversion nanoparticles
    (i) they are dispersed in a concentration between 0.1% and 10% by weight, preferably about 4% by weight.


    In the context of the present invention, "metal alkoxide" means a chemical compound comprising a metal atom M attached to at least one organic group through an oxygen atom (M-OR). Metal alkoxide is formed in situ or ex situ from an inorganic type precursor such as nitrates, chlorides or metal perchlorates, or organic type such as acetates or acetylacetonates. Examples of suitable non-limiting metal alkoxides for the sol-gel synthesis process of the present invention when the metal is for example silicon are tetraethyl orthosilicate (TEOS), methyltriethoxysilane (MTES), methyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane or vinyltriethoxysilane.
    Depending on the desired characteristics for the final composite material, the sol-gel synthesis process is carried out by acid route, preferably using a silicon alkoxide precursor, such as for example silicon chloride, or by basic route, preferably using a precursor of zinc alkoxide, such as zinc acetate. The nature of the alkoxide will determine the pH range in which the condensation of the sun and gel formation will take place (step (iii)).
    The dispersion of step (i) of the sol-gel synthesis process of the present invention may optionally comprise a drying retarding agent.
    In the absence of indications to the contrary, the dispersion components of step (i) listed are widely known to those skilled in the art for sol-gel synthesis processes and can be of the organic or inorganic type.
    The sol-gel synthesis process of the present invention further comprises a step (ii) of adding water to the dispersion of step (i) to give rise to a hydrolysis reaction and formation of a sun.
    In a particular embodiment, step (ii) further comprises the addition of a catalyst that accelerates the hydrolysis reaction. Non-limiting examples of catalysts suitable for the sol-gel synthesis process of the present invention are of the inorganic type, such as hydrochloric acid, and of the organic type, such as ethanolamine.
    The sol-gel synthesis process of the present invention further comprises a step (iii) of condensation of the sun of step (ii) resulting in the formation of a gel. The gel obtained acts as an encapsulating element of the luminescent upconversion nanoparticles of the present invention in a manner that prevents their aggregation.


    In a particular embodiment, the gel formation in step (iii) takes place at a pH between ≤6 and ≥2. The pH can be determined by the acidic or basic nature of the metal alkoxide used in step (i) as defined above.
    The sol-gel synthesis process of the present invention further comprises a step (iv) of aging of the gel obtained in step (iii).
    The aging of the gel favors its homogeneity. A non-limiting example of
    The aging of a gel obtained in step (iii) is the use of a zinc acetate as a precursor to metal alkoxide by heating at 60 ° C for 72 hours in a closed flask to favor the hydrolysis and condensation processes of Zn cations (II).
    Step (iv) of the sol-gel synthesis process of the present invention further comprises drying the aged gel for solvent removal resulting in a luminescent composite material, and comprising heat treatment thereof in a temperature range between 30 ° C and 200 ° C. This process is carried out, for example, in an oven at 60 ° C for 24 hours in a crystallization tray.
    The sol-gel synthesis process of the present invention further comprises a step (v) of densification of the ceramic composite resulting from step (iv) by heat treatment eliminating organic waste from the precursors. The heat treatment is carried out at a temperature between 300 ºC and 600 ºC with a time of
    25 residence between 0.1 to 24 hours.
    In a particular embodiment, the sol-gel synthesis process of the present invention further comprises a step (vi) of conditioning the resulting composite material by grinding to obtain a particle size in a desired size range.
    A non-limiting example is dry milling in a mixing mill using 1 mm diameter stabilized zircon balls for 30 minutes to obtain a powdery material consisting of luminescent nanoparticles of the invention dispersed in a densified sol-gel matrix with a average size where 90% of the particles have a size smaller than 10 µm.


    In a particular embodiment, the luminescent composite material of the invention possesses high resistance to chemical agents and thermal stability, preferably at temperatures ≥400 ° C. These properties allow their application as safety markers as part of paints, in the preparation of functional ceramic materials or as part of coating large surfaces. In another preferred embodiment, the luminescent composite material is colorless, which allows its application as an authentication or quality marker in sectors such as the paper, packaging or textile sector.
    Therefore, a final aspect of the present invention relates to the use of the luminescent composite material as defined above in the sectors of paper, plastic, packaging, textile, automobile, biological, medical-pharmaceutical, document security, tracers, ceramic pigments, Optoelectronics or photovoltaic.
    Examples
    The first part of the experimental section (Examples 1 to 3) refers to the preparation of the nanoparticles of the present invention. The second part of the experimental section (Examples 4 to 7) refers to the evaluation of the stability of the ligand bond to the surface of the nanoparticles of the present invention in acidic media, which is of interest among other applications, for its sol-gel encapsulation. The third part of the experimental section (Examples 8 and 9) refers to the preparation of the composite material of the present invention.
    Example 1: Synthesis of NaYF4: Yb, Er passivated with oleate nanoparticles (UCNP @ oleate) NaYF4: Yb3 +, Er3 + nanoparticles were synthesized following the process described in French-Soriano et al. (Nanoscale 2015, 7, 5140-5146). In particular, a mixture of 0.8 mmol of YCl3 · 6H2O, 0.18 mmol of YbCl3 · 6H2O, 0.02 mmol of ErCl3 · 6H2O (0.02 mmol), 12 mL of oleic acid and 15 mL of octadecene ( ODE) was heated to 160 ° C in a 50 mL flask and continuous stirring. After dissolution of the lanthanide salts (ca. 30 minutes), the mixture was cooled to about 110 ° C and then 10 mL of a solution of methanol, NaOH (2.5 mmol) and NH4F (4.0 mmol) were slowly added ). The mixture was degassed at 100 ° C for 30 min and continued stirring. Finally the mixture was heated at 305 ° C under N2 atmosphere for 1h. Subsequently, the solution was cooled to room temperature and the nanoparticles precipitated by centrifugation (10,000 rpm, 10 min, 25 ° C). The nanoparticles passivated with oleate were washed three times with solutions of (43.5: 40.5: 16 v / v) hexane / acetone / methanol.


    Example 2: Synthesis of NaYF4: Yb, Er naked nanoparticles (UCNPnaked) NaYF4: Yb3 +, Er3 + naked nanoparticles were prepared following the procedure of Capobianco et al. (Nano Lett. 2011, 11, 835-840). In particular, 100 mg of UCNP @ oleate was dispersed in 10 mL of aqueous HCl at pH 4. The mixture was stirred for 2 h and the solution was maintained at pH 4 adding 0.1 M HCl. The oleic acid was removed by extraction with diethyl ether (3 times). All the etheric phases were combined and a re-extraction with water was performed. Oleic acid was combined with all aqueous phases and re-extracted with diethyl ether. The UCNPnaked were recovered from the aqueous phase by precipitation with acetone followed by centrifugation (10,000 rpm, 15 min, 25 ° C). The precipitate was washed three times with acetone and re-precipitated by centrifugation. Finally the UCNPnaked dispersed in Milli Q water.
    Example 3: Synthesis of NaYF4: Yb, Er nanoparticles passivated with 2-chloroacetamide
    (UCNP @ ligand2-chloroacetamide) The UCNPnaked nanoparticles were dispersed in DMF, the medium was basified with sodium hydroxide, and after separation of excess NaOH, the solid 2-chloroacetamide ligand was added to the colloidal solution. After 48h of stirring, the precipitation of the passivated nanoparticles (UCNP @ ligand2-chloroacetamide) was induced by centrifugation, the solid was washed several times and finally dried.
    Example 4: Synthesis of NaYF4: Yb, Er nanoparticles passivated with 2-chloroacetic acid
    (UCNP @ ligand2-chloroacetic) UCNPnaked nanoparticles were dispersed in DMF, the medium was basified with sodium hydroxide, and after separation of excess NaOH, solid 2-chloroacetic ligand was added to the colloidal solution. After 48h of stirring, the precipitation of the passivated nanoparticles (UCNP @ ligand2-chloroacetic) was induced by centrifugation, the solid was washed several times and finally dried.
    Example 5: Stability of UCNP @ ligand2-chloroacetamide in acid medium FTIR (Fourier transform infrared spectroscopy) spectra were obtained for UCNP @ ligand2-chloroacetamide nanoparticles (Figure 1) prepared as described in Example 3, and after 5 and 48 hours in aqueous solution at pH 2. Thus, the UCNP @ ligand2-chloroacetamide nanoparticles showed an insignificant variation of their emissive properties when kept dispersed in water at pH 2 for 48 hours, as can be confirmed in Figure 2b. Subsequently, the UCNP @ ligand2-chloroacetamide nanoparticles are


    precipitated by basification to neutral pH by addition of NaOH and centrifugation, washed with water and dried. Their analysis by FTIR (Figure 1) demonstrates that the organic ligand does not uncoordinate the UCNP nanoparticles @ ligand2-chloroacetamide and its emissive properties remain unchanged (Figure a-d2). Example 6: XPS characterization of the UCNP @ ligand2-chloroacetamide nanoparticles. For comparison of the free and bound ligand, XPS C1s spectra were obtained for the UCNP @ ligand2-chloroacetamide nanoparticles (Figure 3, below) prepared as described in Example 3 and for the free starting ligand, that is, 2- Chloroacetamide (Figure 3, above). The XPS N1s spectra were also obtained for the UCNP @ ligand2chloroacetamide nanoparticles (Figure 4, below) prepared as described in Example 3 and for the starting organic compound 2-chloroacetamide (Figure 4, above).
    It is important to highlight the important changes in the energy values of C1s and N1s between the starting organic compound 2-chloroacetamide and the organic ligand of UCNP @ ligand2chloroacetamide. These displacements are consistent with a chemical reaction between the starting organic compound 2-chloroacetamide and the surface of the nanoparticle which allows the permanence of the ligand on the surface of the nanoparticle in strongly acidic media.
    However, the XPS C1s spectra for the UCNP @ oleate nanoparticles known in the state of the art and prepared according to Example 1 show small changes in relation to the free oleic acid. This fact is also observed for different carboxylic acids, such as, for example, decanoic acid or dodecanedioic acid (Liu Y. et al. Nanoscale 2011, 3, 4804) and demonstrates that the ligand is adsorbed on the surface of the nanoparticle through the group carboxylate. The small variation of energy of the functional group that is adsorbed on the surface of the nanoparticle is a general fact for the nanoparticles described in the state of the art, as shown for example by the XPS N1s spectrum of the free oleylamine that interacts with the nanoparticle by the amino group and has a value of ca. 400 eV in both cases, free and coordinated (Goel,
    V. Thesis 2011, McGill University, Montreal).
    Example 7: XPS characterization of the UCNP @ ligand2-chloroacetic nanoparticles. Similar to Example 6, the XPS C1s spectra for the UCNP @ ligand-2-chloroacetic nanoparticles (Figure 5, below) prepared as described in Example 4 and for the organic 2-chloroacetic starting compound (Figure 2) were obtained for comparison 5, above). XPS O1s spectra were also obtained for UCNP @ ligand2 nanoparticles


    Chloroacetic acid (Figure 6, below) prepared as described in Example 4 and for the starting organic compound 2-Chloroacetic acid (Figure 6, above).
    The important changes in the energy values of C1s and O1s between the starting organic compound 2-chloroacetic acid and the organic ligand of the nanoparticle UCNP @ ligand2-chloroacetic acid should be noted. As with Example 6, this displacement is consistent with a chemical reaction between the starting organic compound 2-chloroacetic acid and the surface of the nanoparticle, which allows the permanence of the ligand on the surface of the nanoparticle in strongly acidic media.
    Example 8: Preparation of a transparent colorless composite material by sol-gel encapsulation in acid medium of UCNP nanoparticles @ ligand2-chloroacetamide.
    For the encapsulation of UCNP nanoparticles @ ligand2-chloroacetamide, a silica sol gel was prepared so that the pigment was dissolved in EtOH at a concentration of 0.6 g / L.
    300 mg UCNP nanoparticles @ ligand2-chloroacetamide were added to 50mL EtOH with stirring and allowed to homogenize for a few minutes. Then, 24 mL of TEOS were added and then 7.2 mL of deionized water was added, dropwise to favor mixing TEOS with water and allowing hydrolysis reactions to occur. Finally, the hydrochloric acid (<0.1 mL) was also added dropwise until a pH of approximately 4 was reached. It was allowed to stir for at least 1 h. The resulting solution was allowed to dry only at room temperature for 48h. Approximately 7.5 g of powder were obtained. The ratio obtained from UCNP @ ligand2chloroacetamide / sol-gel was 1/25 giving a green emission (Figure 7). Comparison of the 1 mg emission of UCNP @ ligand2-chloroacetamide and that of 1 mg of the composite material showed that the composite material is about 25 times more emissive. It follows that the sol-gel treatment increased the emissive capacity of the UCNPs by 625 times.
    Example 9: Preparation of a composite material by a sol-gel synthesis process in basic medium with UCNP @ ligand2-chloroacetamide particles.
    For the encapsulation of UCNP nanoparticles @ ligand2-chloroacetamide, a sol gel was carried out in a basic medium, using a Zn precursor.
    7.5 g of Zinc acetate in 50 mL of ethanol was added under stirring by adding 20 mg of nanoparticles and allowed to homogenize for a couple of minutes until the acetate


    It was dissolved in alcohol. Then the nanoparticle dispersion was added and
    stirred for at least 2 minutes. Next, 3 mL of ethanolamine was added dropwise to
    drop to favor mixing with ethanol and allow reactions to occur with
    Zinc acetate Ethanolamine acts as a catalyst and stabilizer for the solution.
    5 Once ethanolamine has been added, the solution must have a pH of 7 or higher. He let himself shake
    for at least 1h. The resulting solution was allowed to dry at room temperature for
    48 h until most of the ethanol was evaporated. After this time a
    very viscous liquid, which was heat treated at 300 ° C to form the structure
    of ZnO for 1 hour for greater crystallinity and waste disposal. After the 10 heat treatment, approximately 2.8 g of powder with emission of
    Pink color.

    权利要求:
    Claims (38)
    [1]
    one. Luminescent upconversion nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise organic ligands attached to their surface by covalent bonds.
    [2]
    2. Nanoparticles according to claim 1, wherein the organic ligands bound to their surface by covalent bonds comprise a unit -CH2CO-.
    [3]
    3. Nanoparticles according to any one of claims 1 to 2, with an average size ≤500 nm.
    [4]
    Four. Nanoparticles according to any one of claims 1 to 3, wherein the nanoparticles have a core / shell structure.
    [5]
    5. Nanoparticles according to any one of claims 1 to 4, wherein M is Na or Li.
    [6]
    6. Nanoparticles according to any one of claims 1 to 5, wherein RE3 + is Yb3 +, Er3 +, Tm3 +, Gd3 + or combinations thereof.
    [7]
    7. Method of preparation of luminescent upconversion nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise organic ligands attached to their surface by covalent bonds, comprising the steps of:
    a) add to a polar solvent precursor nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is a rare earth ion or combinations thereof; characterized in that said nanoparticles comprise groups -O, -OH, -HOH or combinations thereof on their surface;
    b) add an excess base on the mixture resulting from step (a); Y
    c) after removing the excess base of the mixture resulting from step (b), add a compound of formula X-CH2CO-Z where X is a halogen, Z is -H, -R, -COR, -OH,

    - OCOR, -NH2, -NHR, -NR2, -NHCOR, -SR or -SCOR, and R is a linear or branched alkyl chain.
    [8]
    8. Method of preparing the nanoparticles according to claim 7, wherein the
    The polar solvent of step (a) is dimethylformamide, acetonitrile, tetrahydrofuran or mixturethereof.
    [9]
    9. Method of preparation of the nanoparticles according to any of claims 7
    to 8, where step (a) takes place at a temperature from about 25 ° C to about 10 of 80 ° C.
    [10]
    10. Method of preparing the nanoparticles according to any of claims 7 to 9, wherein the excess base of step (b) is an inorganic base, preferably NaOH.
    [11]
    eleven. Method of preparing the nanoparticles according to any one of claims 7 to 10, wherein Z is -H, -NH2 or -OCOR in the compound of step (c) of formula X-CH2CO-Z.
    [12]
    12. Method of preparing the nanoparticles according to claim 11, wherein the
    The compound of formula X-CH2CO-Z in step (c) is 2-chloroacetamide or 2-chloroacetic acid.
    [13]
    13. Luminescent upconversion nanoparticles of formula MLnF4: RE + 3, where M is an alkali metal, Ln is a lanthanide element or an analog thereof and RE + 3 is an ion of
    25 rare earths or combinations thereof; and comprising organic ligands bound to their surface by covalent bonds, obtainable by the method of preparation according to any one of claims 7 to 12.
    [14]
    14. Use of the luminescent upconversion nanoparticles according to any one of claims 1 to 6 and 13 as fluorescent markers or photosensitizers.
    [15]
    15. Use of the luminescent upconversion nanoparticles according to claim 14 in the biological or medical-pharmaceutical sector.
    16. Luminescent composite material comprising the luminescent upconversion nanoparticles according to any of claims 1 to 6 and 13.

    [17]
    17. Luminescent composite material according to claim 16, wherein the composite material is ceramic.
    18. Luminescent composite material according to any of claims 16 and 17, wherein the composite material is transparent.
    [19]
    19. Luminescent composite material according to any of claims 16 to 18, obtainable by a sol-gel synthesis process.
    [20]
    twenty. Use of the luminescent composite material according to any of claims 16 to 19 as a fluorescent marker or photosensitizer.
    [21]
    twenty-one. Use of the luminescent composite material according to any of claims 16 to
    15 20 in the paper, plastic, textile, automobile, biological, medical and pharmaceutical, document security, plotters, ceramic pigments, optoelectronics or photovoltaic sectors.

    Figure 1
    26

    [3]
    3.5
    [3]
    3.0
    [2]
    2.5
    [2]
    2.0
    1.5
    1.0
    [0]
    0.5
    [0]
    0.0
    UCNPs @ ligand pH 7.53 (control)
    2-Chloroacetamide
    I.F. I.F.
    350 400 450 500 550 600 650 700 Wavelength (nm)
    [3]
    3.0
    [2]
    2.5
    [2]
    2.0
    1.5
    1.0
    [0]
    0.5
    [0]
    0.0
    UCNPs @ ligand
     pH 2.00
    2-Chloroacetamide
    350 400 450 500 550 600 650 700 Wavelength (nm)
    Figure 2

    I.F.
    I.F.
    [2]
    2.5
    [2]
    2.0
    1.5
    1.0
    [0]
    0.5
    [0]
    0.0
    Wavelength (nm)
    [2]
    2.5
    [2]
    2.0
    1.5
    1.0
    [0]
    0.5
    [0]
    0.0
    Figure 2 (cont.)

    Counts / s
    Counts / s
    Wavelength (nm)
    Figure 3

    Counts / s
    2500 2000 1500 1000 500 0
    392 394 396 398 400 402 404 406 Wavelength (nm)
    2500 2000
    Counts / s
    150010005000
    Figure 4

    80000 70000 60000
    Counts / s
    50,000 40,000 30,000 20,000 10,000 0
    UCNPs @ ligand 2-chloroacetic-C 1s






    Counts / s
    280 285 290 295 Wavelength (nm)
    Figure 5

    Counts / s
    2-Chloroacetic acid-O1s
    525 530 535 540 Wavelength (nm)
     UCNPs @ ligand-O1s
    2-chloroacetic
    Counts / s
    525 530 535 540 Wavelength (nm)
    Figure 6

    Figure 7
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