CN101955774A - Nanocrystalline painted plant - Google Patents
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- CN101955774A CN101955774A CN2009110002888A CN200911000288A CN101955774A CN 101955774 A CN101955774 A CN 101955774A CN 2009110002888 A CN2009110002888 A CN 2009110002888A CN 200911000288 A CN200911000288 A CN 200911000288A CN 101955774 A CN101955774 A CN 101955774A
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Abstract
The present invention relates to contain at least a nanocrystalline plant, when described plant is exposed to light time of specific wavelength, described plant is by described nanocrystalline a kind of specific color or the multiple color of launching.On the other hand, the present invention relates to carry out painted method with at least a nanocrystalline outside surface to plant.The invention still further relates to at least a nanocrystalline tissue and carry out painted method plant.
Description
Technical field
The present invention relates to contain the plant of at least a nanocrystalline (nanocrystal), when with the rayed of a certain wavelength, by described nanocrystalline, this plant sends a kind of particular color or multiple color.Another aspect of the present invention relates to at least a nanocrystalline outside surface to plant (outer surface) and carries out painted method.The invention still further relates to at least a nanocrystalline tissue and carry out painted method plant.
Background technology
Semiconductor nano (quantum dot (quantum dot)) all receives great concern on basis and technological layer, and they can be applicable in the multiple technologies, for example: and luminescent device (Colvin etc., Nature 370,354-357,1994; Tessler etc., Science 295,1506-1508,2002), laser (Klimov etc., Science 290,314-317,2000), solar cell (Huynh etc., Science 295,2425-2427,2002) or in Biochemical Research field (as cytobiology) as the biological mark.For example, ask for an interview Bruchez etc., Science, the 281st volume, 2013-2015 page or leaf, 2001; Chan ﹠amp; Nie, Science, the 281st volume, 2016-2018 page or leaf, 2001; Klarreich is at Nature, the 43rd volume, and the 450-452 page or leaf, the U.S. Patent No. 6,207,392 of summary in 2001; Also ask for an interview Mitchell, Nature Biotechnology, the 1013-1017 page or leaf, 2001, and U.S. Patent No. 6,423,551,6,306,610 and 6,326,144.
The characteristics of luminescence of quantum dot brilliance is derived from quantum size confinement (quantum size confinement), when metal and semiconductive core particle (core particle) excite the little about described quantum size confinement that occurs 1 to 5nm time of Bohr radius (excitationBohr radii) than them.(Alivisatos, Science, 271,933-37,1996; Alivisatos, J.Phys.Chem.100,13226-39,1996; Brus, Appl Phys., A53,465-74,1991; Wilson etc., Science, 262,1242-46,1993).
Studying the most deep semiconductor nano material is sulphur system's (chalcogenide) II-VI material and III-V material.To the interested major cause of these semiconductor nano materials is to make photoluminescence cross over whole visible spectrum by the control particle diameter.
Consider above-mentioned mentionedly, wish further to use for nanocrystalline searching.
Description of drawings
With reference to detailed description and when the present invention may be better understood in conjunction with non-restrictive example and accompanying drawing.
Fig. 1 has shown a kind of orchid, promptly spends dendrobium (Dendrobium White Fairy) in vain, and this orchid is carried out dip coated (dip coat) in containing the nanocrystalline solution of CdZnSe.This picture shows, the described orchid under the UV lamp has at 302/345nm and excites.Compare with natural white/purple of the described orchid that shows in the less picture in place, Fig. 1 upper left side, after the dipping, the flower of this orchid presents orange in described solution.
The phial that Fig. 2 shows in upper left picture is equipped with solution, and it is nanocrystalline that described solution contains the CdZnSe that is dissolved in the octadecylene.Top-right picture has shown the nanocrystalline stem of noble dendrobium of spending in vain for white before of stem (stem) the picked-up CdZnSe by plant.The picture of below has shown picked-up CdZnSe orchid after nanocrystalline and that shine with ultraviolet (UV) lamp, and this orchid has at the 302/345nm place and excites.Orchid after the above-mentioned dyeing has the color identical with orchid shown in Figure 1, and is promptly orange.
Fig. 3 is equipped with the aqueous solution that contains fluorescent yellow (fluorescein) at the phial that upper left picture shows.Top-right picture has shown by the stem of noble dendrobium of spending in vain for white before the plant roots picked-up fluorescent yellow.The picture of below has shown orchid after the picked-up fluorescent yellow and that shine with the UV lamp, and this orchid has at the 302/345nm place and to excite.Orchid after the above-mentioned dyeing presents green, and wherein, color concentrates on vascular bundle (vascular strand), and vascular bundle also is known as vein (leave vein) or vein net (leave vein network).
Fig. 4 a has shown that picked-up fluorescent yellow and the CdZnSe polychrome after nanocrystalline spends the stem of noble dendrobium in vain.In Fig. 4 a, ovary (ovary) zone is visible nanocrystalline orange, and is visible slightly nanocrystalline orange at petal and sepal base portion (base), and under the fluorescence of fluorescent yellow, vein presents green.Fig. 4 b has shown the transverse section of stem.Fig. 4 b has shown the real color image based on 32 passages (channel)/32 colour gamut (color range).6 gray points (Fig. 4 c is clearer) around the center of the section of described stem are green under the fluorescence of fluorescent yellow, and peripheral part is owing to nanocrystalline luminous of CdZnSe presents orange.Fig. 4 c has shown the same cross section of described stem, but has been to use colour filter, only shown the light that is sent by fluorescent yellow (c), and Fig. 4 d has only shown the nanocrystalline light that sends by CdZnSe.
Embodiment
First aspect the present invention relates to a kind of plant that contains or be combined with at least a nanocrystalline (quantum dot).Depend on and be used for described plant is carried out painted nanocrystalline, contain or be combined with the light of the plant emission specific wavelength of semiconductor nano material.
Term " plant " comprises cell and also contains the biology of plastid except that containing nucleus (having double-core film (double nucleusmembrane) and some karyomit(e)s).Plastid exists with the chloroplast(id) form, perhaps can be transformed into chloroplast(id) under appropriate condition.Different with all other heterotrophs with animal, green plants is a phototrophy.Cyanobacteria) or unicellular be used for described term plant of the present invention and do not comprise that (for example:, described unicellular organism also is classified as plant to unicellular organism sometimes.Plant of the present invention has also got rid of liver moss, lichens and fungi, although fungi does not have plastid, also fungi is classified as plant sometimes.
In another aspect of this invention, describedly nanocrystallinely can also be contained in dried plant or the synthetical plant or on dried plant or the synthetical plant.This means that the term plant of using refers to that not only lived plant also can refer to not have plant life or that lost life herein.Such plant comprises dried plant and synthetical plant.The plant that further is elaborated below plant of further mentioning below described dried plant can be selected from or the part.Artificial plant is generally used for decorative purpose, and the mixture of usable polymers or mixture of polymers, paper or plate (laminated or no lamination), tinsel or above-mentioned materials is made.Described artificial plant can be a kind of replica in the following listed plant or a kind of new form of new-create plant, and described plant does not exist with this form at occurring in nature.
Artificial plant can by the silk of silk, artificial silk (artificial silk of making by the mixture of for example regenerated fiber (rayon), mercerized cotton, polyester or these mixtures of material or regenerated fiber and silk), polymer modification (for example: the silk of collagen modification), the cotton of polymer modification (for example: mercerized cotton) or purified polymer (for example: nylon, polymeric amide or polyester) make.
One kind of plant contains the multiple outwards organ of raised growth.Such organ comprises root, Ye Hehua.In one aspect of the invention, the described nanocrystalline gas that is contained in or is incorporated into plant is given birth to (aerial) part, and described gas first portion refers to the part on the soil that this plant grows of being present in of plant, for example stem, branch, Hua Heye.In an example, described gas first portion refers to flower or the leaf of plant.
In the example, above-mentioned plant of the present invention is the plant that blooms, and promptly opens the plant of at least once spending or have at least one florescence in the specified phase of plant life.Phrase " plant that blooms " be often referred to have root, transfusion tissue (conductive tissue) (xylem and phloem) that stem, leaf and growth are intact surpass in 250000 kinds the angiosperm (belonging to Magnoliophyta (Magnoliophyta)) any one.The general seed that passes through to be produced is in the chamber of the closure in the flower (ovary) and angiosperm and gymnosperm is distinguished, and still, this difference is not under any circumstance be not always the case clearly (clear-cut).Angiospermae comprises two guiding principles: unifacial leaf guiding principle (monocots) and dicotyledonous guiding principle (dicots).The petal of unifacial leaf guiding principle (flower parts) is 3 multiple (in threes), and conduit (conducting strand) is dispersed in stem, mostly is parallel venation in the leaf, and does not have form layers.The petal of dicotyledonous guiding principle is 4 or 5 multiple, and conduit is arranged in column (cylinder), is reticulate venation in the leaf, and a form layers is arranged.The plant that blooms is in habit, size and show great diversity in shape; The plant that blooms has surpassed 300 sections, grows in each continent, comprises the Antarctica.The plant that blooms almost can adapt to various living environments.The plant that major part is bloomed is by carrying out the specificity breeding and carry out sexual propagation being present in organ in all flowers by means of seed.
In one aspect of the invention, the described plant that blooms includes but not limited to from following plant: the Rosaceae (rosaceae), silk ball section (hydrangeaceae), the orchid family (orchidaceae), silk ball section (hydrangeaceae), hyacinthaceae (hyacinthaceae), Begoniaceae (begoniaceae), Labiatae (lamiaceae) (comprising that for example lavandula angustifolia belongs to (genus lavandula)), composite family (asteraceae) (comprising for example dahlia (genus dahlia) and Gerbera (genus gerbera)), Mang ox seedling section (geraniaceae) (comprising for example Pelargonium (genus geranium)), Solanaceae (solanacead) (comprising for example Petunia (genus petunia)), Liliaceae (liliaceae) (comprising for example Tulipa (genus tulipa)), Primulaceae (primulaceae) (comprising for example primula (genusprimula) and Cyclamen (genus cyclamen)), Oenotheraceae (onagraceae), Violaceae (violaceae), Gesneriaceae (gesneriaceae), Malvaceae (malvaceae) (comprising for example hibiscus (genus hibiscus)), Bromelia family (bromeliaceae), Araeceae (araceae) (comprising for example Anthurium (genus anthurium)), Ericaceae (ericaceae) (comprising for example Rhododendron (genus rhododendron) (comprising rhododendron (azealeas))), Theaceae (theaceae) (comprising for example Camellia (genus camellia)) or Nyctaginaceae (nyctaginaceae) (comprising for example bougainvillea (genus bougainvillea)).
In an example, described plant includes but not limited to: rose, orchid, laurustinus (hydrangea), jacinthe, Flower of Evans Begonia, lavandula angustifolia, Garden Dahlia, Flos Pelargonii, petunia, turmeric, flower of Greenish Lily, Flower of Beltleaf Primrose, violet (viola), Herba Leibnitziae, gloxinia (gloxinia), the rose of Sharon, pineapple (bromeliad), Cyclamen persicum, the red palm (anthurie), rhododendron, Flower of Lesser Bougainvillea (bougainvillea) or Flower of Japanese Camellia.
The orchid family comprises orchid (Orchidoideae) subfamily, tree orchid (Epidendroideae) subfamily, Herba vanillae Planifoliae (Vanilloideae) subfamily, lady's slipper (Cypripedioideae) subfamily and intends blue (Apostasioideae) subfamily.Lady's slipper (Cypripedioideae) subfamily for example comprises: lady's slipper (Cypripedieae) family, Mexico footwear orchid (Mexipedieae) family, America pocket orchid (Phragmipedieae) family and Xi Lini footwear orchid (Selenipedieae) family.Tree orchid (Epidendroideae) subfamily for example comprises: tree orchid (Arethuseae) family, spoon lip orchid (Calypsoeae) family, its (Cryptarrheneae) family of gram Lay, Pseudobulbus Coelogynes corymbosae (Coelogyneae) family, tree orchid (Epipogieae) family, tiger tongue orchid (Epipogieae) family, rhizoma Gastrodiae (Gastrodieae) family, natural pond orchid (Malaxideae) family, Bird's Nest orchid (Neottieae) family, handle lip orchid (Podochilaeae) family, culm orchid (Tropidieae) family and Ai Keseluo (Xerorchideae) family.Herba vanillae Planifoliae (Vanilloideae) subfamily for example comprises: Zhu Lan (Pogoniinae) and vanilla (Vanilleae) subfamily.Blue (Orchidoideae) subfamily for example comprises: Di Sela (Diceratosteleae) family, Ke Dengnuo (Codonorchideae) family, skull orchid (Cranichideae) family, Diseae family, Diurideae family and blue family.
Handle lip orchid (Podichileae) family of above-mentioned tree orchid (Epidendroideae) subfamily for example comprises: dendrobium (Dendrobiinae) subtribe, dendrobium (Dendrobiinae) subtribe comprise for example blocks that Derain (Cadetia) belongs to, the stem of noble dendrobium (Dendrobium) belongs to, brown stem orchid (Diplocaulobium) belongs to, thick lip orchid (Epigeneium) belongs to, spend orchid (Flickingeria) to belong to temporarily and Pu Sede (Pseuderia) genus.For example, a kind of orchid of using in an example of the present invention " is spent the stem of noble dendrobium (DendrobiumWhite Fairy) in vain " and belongs to Dendrobium.
The nanocrystalline type of using among the present invention can contain semiconductor material or martial ethiops (magnetic oxide) or be made up of semiconductor material or martial ethiops, and described martial ethiops comprises ternary or higher system, for example: the metallic iron oxysome.The emission of these nanocrystalline (quantum dots) can be regulated by composition and/or size.
Be used for plant is carried out painted at least a nanocrystalline can including but not limited to:
The metal oxide that rare earth is metal-doped, the chemical formula of this metal oxide are MeAl
2O
4: Re or Me
4Al
14O
25: R; Or
Bielement nano crystalline substance, the chemical formula of this bielement nano crystalline substance are M1A or M1O; Or
Ternary nanocrystals, the chemical formula of this ternary nanocrystals are M1M2A or M1AB or M1M2O; Or
Quaternary nanocrystals, the chemical formula of this quaternary nanocrystals are M1M2AB;
Wherein, M1 in described bielement nano crystalline substance, ternary nanocrystals, the quaternary nanocrystals and M2 are a kind of metal independently, and described metal is for example from II family, III-th family, IV family or group VIII in the periodic system of elements (PSE); And if exist, A and B are for example from the VI family among the PSE or the element of V family independently of each other; And
Wherein, the Me in the adulterated metal oxide of described rare earth metal for example can comprise: Ca, Sr or Ba; And
Re in the adulterated metal oxide of described rare earth metal is at least a element, and this element can comprise Tb, Dy, Nd, Eu or Tm.
The adulterated metal oxide of rare earth metal is well known in the art, and is for example describing in detail among US 6264855, JPH9-143463, JP 2543852, JP 2697733, JP 2697688, JP H10-273654, the JP 2929162.In brief, the adulterated metal oxide of aforesaid rare earth metal can be water-proof and can for example make by the following method: with at least a acidic cpd to carrying out acid treatment as raw-material luminous pigment, described acidic cpd can be no more than acidic compound under 3 the condition for a kind of acid or at pH, carry out alkaline purification with at least a basic cpd then, described basic cpd can be the compound that produces alkali under the condition of 4-9 for a kind of alkali or at pH.
If luminous pigment is a kind of luminous pigment that is doped with at least a thulium, matrix of oxide in the described luminous pigment (matrix) contains the element of at least a for example Mg, Ca, Sr, Ba and Zn and the element of at least a for example B, Al, P or Ga, and then the luminous pigment as acid-treated object can be various types of luminous pigments.The doping of described rare earth element is not particularly limited, but 0.0001-30 weight % is enough, and perhaps in an example, with respect to the total amount of luminous pigment, 0.1-10 weight % is enough.
The example of luminous pigment comprises that general formula is MeAl
2O
4: Re or Me
4Al
14O
25: the compound of R.In described general formula, Me can be Ca, Sr and Ba; And the Re in the metal-doped metal oxide of rare earth is at least a element, and described element is Tb, Dy, Nd, Eu and Tm for example.Preparation to the adulterated metal oxide of above-mentioned rare earth metal in US6264855 for example describes in detail.
Chemical formula is that the example of the bielement nano crystalline substance of M1A or M1O is well known in the art.M1 in the following formula can be according to II family, III-th family, IV family, VII family or group VIII metal in the periodic system of elements of the system of traditional International Union of Pure and Applied Chemistry (IUPAC) (Periodc System of Elements).According to new IUPAC system, corresponding family (being traditional system in the bracket) is the 2/12nd family (II family), the 13rd family (III-th family), the 14th family (IV family), the 7th family (VII family).The suitable example of II family (new IUPAC system is the 12nd family) is Cd, Zn and (the 2nd family of new IUPAC system) Mg, Sr, Ca and Ba.The suitable example of III-th family (the 13rd family of new IUPAC system) is Al, Ga and In.Two illustrative example of the element that IV family (the 14th family of new IUPAC system) is suitable are Pb and Sn.An illustrative example of the element that VII family (the 7th family of new IUPAC system) is suitable is Mn.The suitable example of group VIII (the 8th family of new IUPAC system) element is Fe, Co, Ni and Ir.In an example of the present invention, in the preparation of bielement nano crystalline substance, got rid of the use of Pb and Cd.
Usually, M1 or suitably the time M1 and M2 can be for example II family, III-th family, IV family, VII family or group VIII separately, II family such as Cd, Zn, Mg, Sr, Ca or Ba, III-th family such as Al, Ga and In, IV family such as Pb, Sn, VII family such as Mn, group VIII such as Fe, Co, Ni or Ir.
A in the above-mentioned formula can be chalcogen or pnicogen (pnictogen), is VI family in the periodic system of elements or V group element according to the IUPAC nomenclature in past promptly or is the 16th family or the 15th family's element according to new IUPAC nomenclature.Like this, the reaction mixture that is used to prepare this type of bielement nano crystalline substance can comprise the metal precursor that contains metal M 1 and elements A.Metal precursor can comprise salt, and described salt provides corresponding metal in nanocrystalline forming process.Described salt for example can for the inorganic salt of corresponding metal (for example: carbonate) or organic salt (for example: acetate, stearate or oleate).Wherein, two kinds of metals or metal precursor are used to prepare this type of binary nanocrystal system, and for example: cadmium and zinc or their oxide compound, above-mentioned two kinds of metal/presomas exist with the ratio of any expection.
Elements A and suitably the time element B can be independently selected from VI family in the periodic system of elements or the V family in the periodic system of elements, VI family such as S, Se, Te, O, V family such as P, Bi or As.
The metal precursor that is used to prepare described bielement nano crystalline substance can be metal oleate salt.Described metal oil hydrochlorate can include but not limited to cadmium oleate, zinc oleate cadmium (cadmium zinc oleate), lead oleate, manganese oleate, magnesium oleate, cadmium oleate lead (cadmium lead oleate), magnesium oleate iron (magnesiumferrous oleate), oleic acid ferromanganese (manganese ferrous oleate), calcium oleate iron (calciumferrous oleate), oleic acid zinc-iron (zinc ferrous oleate), oleic acid strontium iron (strontium ferrousoleate), oleic acid ferro-cobalt (cobalt ferrous oleate) or oleic acid ferronickel (nickel ferrous oleate).
The example of bielement nano crystalline substance includes but not limited to CdSe, CdTe, CdS, PbSe, PbTe, PbS, SnSe, ZnS, ZnSe or ZnTe.General formula is that the bielement nano crystalline substance of M1O for example can be formula CdO, PbO, MnO, CoO, ZnO or FeO.It should be noted that herein expression formula M1A and M1O only for illustrate this nanocrystalline be binary, show that they contain two kinds of elements.Expression formula M1A and M1O do not represent described nanocrystalline stoichiometric ratio (although described nanocrystallinely can be CdSe or CdO, only enumerate two examples) inevitably,, expression formula M1A and M1O can comprise that also stoichiometric ratio is MO
2(for example: MnO
2), M
2O
3(for example: Al
2O
3) or M
3O
4(for example: Fe
3O
4) nanocrystalline.
Some studies show that can improve by the lower slug particle (core particle) of band gap of sealing adjustable size with the higher inorganic materials shell of band gap (band gap) nanocrystalline luminous.For example, the CdSe quantum dot of usefulness ZnS layer passivation is strong luminescence at room temperature, and can be adjusted to redness from blueness by changing their emission wavelength of size of particles.And the sputtering ZnS encapsulated layer makes surface non-radiative spot (nnonradiative recombination site) passivation, thereby makes described nanocrystalline (quantum dot) more stable.(Dabbousi etc., J.Phys.Chem.B101,9463-75,1997.Kortan etc., J.Am.Chem.Soc.112,1327-1332,1990).
The general formula of ternary nanocrystals can be M1M2A.M1 in the following formula and M2 are the metal of II family, III-th family, IV family, VII family or group VIII in the periodic system of elements independently.A can be VI family or the V group element in the periodic system of elements.In other example, the general formula of ternary nanocrystals can be M1AB.M1 in the following formula can be the metal of II family, III-th family, IV family, VII family or group VIII in the periodic system of elements.A and B can be the V family in the periodic system of elements or the element of VI family independently.In the another one example, the general formula of the ternary nanocrystals that the method according to this invention forms can be M1M2O.M1 and M2 can be the metal of II family, III-th family, IV family, VII family or group VIII in the periodic system of elements independently.O is an oxygen.Ternary nanocrystals can be various structures.Described ternary nanocrystals for example can be laminate structure (as core/shell structure), and perhaps described ternary nanocrystals can be (homogenous) uniformly, for example: have uniform composition or gradually change or composition that successive (stepless) changes.
The general formula of the quaternary nanocrystals that forms can be M1M2AB.As defined above, M1 and M2 can be the metal of II family, III-th family, IV family, VII family or group VIII in the periodic system of elements.A and B can be the V family in the periodic system of elements or the element of VI family independently.
General formula is that the illustrative examples of the ternary nanocrystals of M1M2A includes but not limited to: molecular formula is the ternary nanocrystals of ZnCdSe, CdZnS, CdZnSe, CdZnTe, SnPbS, SnPbSe and SnPbTe.General formula is that the illustrative examples of the ternary nanocrystals of M1AB can comprise that molecular formula is the nanocrystalline of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe and PbSTe.General formula is that the illustrative examples of the ternary nanocrystals of M1M2O can comprise that general formula is M1M2
2O
4Nanocrystalline, for example: ferrite MgFe
2O
4, CaFe
2O
4, SrFe
2O
4, ZnFe
2O
4, NiFe
2O
4, CoFe
2O
4And MnFe
2O
4It is also to be noted that herein expression formula M1M2A, M1AB and M1M2O be only used for illustrating these nanocrystalline be ternary, show that they contain three kinds of different elements.Correspondingly, from expression formula M1M2A, M1AB and M1M2O, nanocrystalline stoichiometric ratio be can not draw,, for example CdZnSe, CdSeTe or MgFe are being even in the example of some randomness
2O
4Embodiment in, nanocrystalline stoichiometric ratio can quite accurately be indicated in the general formula.Therefore, above-mentioned formula M 1M2A, M1AB and M1M2O comprise that also for example stoichiometric ratio is M1
1-xM2
xA (for example: Cd
1-xZn
xSe), M1
xM2
1-xA (for example: Zn
xCd
1-xSe) or M1
xA
yB
1-y(for example: CdSe
yS
1-y), M1
xA
1-yB
y(for example: CdSe
1-yS
y) or M1
1-xM2
xO (for example: Mg
1-xF
ExO) or M1
xM2
1-xO (for example: Fe
xMn
1-xO) nanocrystalline.
General formula is that the illustrative examples of the quaternary nanocrystals of M1M2AB can comprise that CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe's is nanocrystalline.It is also to be noted that, herein expression formula M1M2AB only for illustrate this nanocrystalline be quaternary, show the described nanocrystalline four kinds of elements that contain.Above-mentioned expression formula M1M2AB does not represent this nanocrystalline stoichiometric ratio (even described nanocrystalline when the CdZnSeS, just list and give one example) inevitably, and comprises that stoichiometric ratio is M1
1-xM2
xA
yB
1-y(for example: Cd
1-xZn
xSe
yS
1-y) or M1
1-xM2
xA
1-yB
y(for example: Cd
1-xZn
xSe
1-yS
y) nanocrystalline.
For example, at the J.Am.Chem.Soc. of Zhong etc., 2003125,8598-8594, the J.Am.Chem.Soc. of Zhong etc., 2003125,13559-13553 or International Patent Application WO 2004/054923 have been described uniform ternary nanocrystals (M1
1-xM2
xA) or quaternary nanocrystals (M1
1-xM2
xA
yB
1-y) example.
Be also to be noted that no matter be bielement nano crystalline substance, ternary nanocrystals or quaternary nanocrystals, during independent the use, describedly nanocrystallinely can be the structure of various needs.Nanocrystallinely for example can be laminate structure, as core/shell structure or nuclear-body-shell structure (core-mantle-shell structure), (Hines, M.A.; Guyot-Sionnest, P., J.Phys.Chem. (1996) 100, and 468; Dabbousi, B.O. etc., J.Phys.Chem.B (1997) 101, and 9463; Peng, X. etc., J.Am.Chem.Soc. (1997) 119,701916-18) or for various alloy structures (for example seeing United States Patent (USP) 7056471), described alloy structure comprises alloy gradient-structure (alloy-gradient structure) (Foley, J etc., Materials ScienceForum, 225-227 rolls up (1996) 323-328 page or leaf) or " body construction (mantel structure) ", described " body construction " has by the nuclear of the alloy layer of relative thin and shell encirclement, put down in writing among the PCT application PCT/SG2008/000290 " Pcrocess Of Forming A Cadmium And SeleniumContaining Nanocrystalline Composite And Nanocrystalline Composite ObtainedTherefrom " as co-applications.
Describedly nanocrystallinely can use following method to make, described method comprises:
(i) form uniform reaction mixture, this uniform reaction mixture contains metal precursor, elements A and lower boiling non-polar solvent, and described metal precursor contains metal M 1, and
(ii) under high pressure, described uniform reaction mixture is placed be suitable for forming under the nanocrystalline high temperature.
In the method, the boiling point of described lower boiling non-polar solvent under normal atmosphere (1013 millibars (mbar)) is lower than about 100 ℃ or 80 ℃.The example of this kind solvent includes but not limited to: hexane, chloroform, toluene, benzene, heptane, hexanaphthene, methylene dichloride, pyridine, tetracol phenixin, dithiocarbonic anhydride, dioxane, ether, diisopropyl ether and tetrahydrofuran (THF) and their mixture.
Also can add tensio-active agent in the method, for example: organic carboxyl acid, organophosphate, organic phospho acid, organo-phosphine oxide, organic amine or their mixture.Embodiment 2 has provided and has prepared this type of nanocrystalline example.
Water-solubility nanocrystalline
In an example of the present invention, the nanocrystalline of use is water miscible.Water-solubility nanocrystalline is known in the art and for example is recorded among WO 2006/118543, the WO 2006/118542 and WO2006/075974.
In addition, it is nanocrystalline that the open WO 00/17656 of PCT discloses nuclear-shell, and this nuclear-shell is nanocrystalline to be respectively SH (CH with molecular formula
2)
n-COOH and SH (CH
2)
n-SO
3Carboxylic acid or the sulfoacid compound of H cover so that nanocrystalline be water miscible.Similarly, asking GB 2342651 to put down in writing in PCT application WO 00/29617 and the English Patent is connected to organic acid on the nanocrystalline surface, so that it is described nanocrystalline for water miscible and be suitable for combining with biomolecules, described organic acid is Thiovanic acid or sulfydryl undecanoic acid for example, and described biomolecules is protein or nucleic acid for example.UK Patent Application 2342651 has also been put down in writing use tri octyl phosphine (trioctylphosphine) as covering material (capping material), thinks that tri octyl phosphine can give nanocrystalline with water-soluble.
In another part document, the open WO 00/27365 of PCT has reported and has used diamines yl carboxylic acid or amino acid as nanocrystalline water solubilizer (water-solubilising agent).The open WO00/17655 of PCT discloses the solubilizing agent that has hydrophilic segment and a hydrophobic part by use to be made nanocrystalline for water miscible.Described solubilizing agent by described hydrophobic grouping be connected to nanocrystalline on, it is water-soluble that described hydrophilic radical then provides, described hydrophilic radical is carboxylic acid or methacrylic acid for example.Water miscible semiconductor nano has been described in another PCT application (WO02/073155), wherein, will be for example the various molecules of trioctylphosphine oxide (TOPO) hydroxamate (trioctylphosphine oxide hydroxamate), hydroxamic acid derivs or multiple tooth complexing agent (as quadrol) be directly connected on the nanocrystalline surface so that this nanocrystalline be water miscible.These are nanocrystalline can be connected on the protein by impulsive discharge sintering method (EDC) subsequently.In another approach, PCT application WO 00/58731 discloses and has been used for the nanocrystalline of hemocyte colony (population) analysis, wherein, with molecular weight for the amino deutero-polysaccharide (amino-derived polysaccharide) of about 3000-3000000 is connected to nanocrystalline on.
United States Patent (USP) 6699723 discloses the compound that uses based on silane as linking agent, thereby is convenient to biomolecules is connected on the luminous nanocrystal probes described biomolecules biological example element and streptavidin.U.S. Patent application No.2004/0072373A1 has described the biochemical marker method of a kind of use based on the compound of silane.The nano particle that will be connected with silane by molecular imprinting is attached on the template molecule, carries out polymerization then to form matrix (matrix).After this, from described matrix, remove described template molecule.The cavity that forms on described matrix owing to remove described template molecule has the character that can be used for mark.
Recently, reported that the use synthetic polymer comes stable water soluble nanocrystalline.U.S. Patent application No.2004/0115817A1 has described, by hydrophobic interaction can with the amphipathic diblock polymer with non covalent bond be connected to nanocrystalline on, described nanocrystalline surface is covered by the reagent place of for example tri octyl phosphine or trioctylphosphine oxide (TOPO) (trioctylphosphine oxide).Similarly, Gao etc. (NatureBiotechnology, the 22nd volume, 969-976, in August, 2004) disclose water miscible semiconductor nano, by non-covalent hydrophobic interaction, encapsulate described semiconductor nano with the amphipathic triblock copolymer.
1, in an example, water miscible nanocrystalline in order to obtain, will cover reagent (cappingreagent) and be connected on the nanocrystalline surface.Described covering reagent and water soluble molecules form host and guest's complex compound.
Can use the surface can with cover the various nanocrystalline of reagent react, water miscible nanocrystalline to obtain, described covering reagent has (end) group that nanocrystal (surface) is had affinity.Correspondingly, the common and nanocrystalline surface of described covering reagent forms covalent linkage.If nanocrystalline, common between described covering reagent and nanocrystalline shell, form covalent linkage for nuclear-shell.If use uniform ternary or quaternary nanocrystals, between the surface of uniform core and described covering reagent, form covalent linkage as describing among the WO2004/054923.The character of described covering reagent can depend on for example hydrophobicity of the internal cavities of host molecule (or wetting ability) for hydrophilic substantially or hydrophobic substantially.In this regard, it should be noted, in the meaning of term " molecule that (substantially) is hydrophobic ", also comprise such molecule, except that hydrophobic part, this molecule can also contain hydrophilic segment, as long as not influencing the hydrophobic part of this molecule (that is, covering reagent), described hydrophilic segment do not get final product with host molecule formation host and guest complex compound with hydrophobic internal cavities.Similarly, term " (substantially) hydrophilic molecules " comprises such molecule, except that hydrophilic segment, this molecule can also contain hydrophobic part, as long as not influencing the hydrophilic segment of this molecule (that is, covering reagent), described hydrophobic part do not get final product with host molecule formation host and guest complex compound with hydrophilic internal cavities.
In an example, the molecular formula that is used for the covering reagent of " surface coverage (surface capping) " is:
H
AX-Y-Z，
Wherein, X is the end group that is selected from S, N, P or O=P, A is 0 to 3 integer, Y is the group with at least three backbone atoms, and Z is the hydrophobicity end group, and this hydrophobicity end group can form Subjective and Objective clathrate complex (host-guest inclusioncomplex) with suitable host molecule (host molecule).
Typically, the Y group of described covering reagent contains 3-50 backbone atoms.Described Y group can mainly contain the various suitable group of giving the outstanding hydrophobic property of described reagent.The example that can be used for the suitable group among the Y comprises: alkyl group (for example: CH
2-), group of naphthene base (for example: cyclohexyl), ether group (for example :-OCH
2CH
2-) or aromatic group (for example: phenyl ring or naphthalene nucleus), only listed small number of examples.Described group Y can be straight chain or side chain, and the substituting group that replaces backbone atoms can be arranged also.Z can be-CH
3, phenyl (C
6H
5) ,-SH, hydroxyl (OH), acidic-group are (for example :-SO
3H, PO
3H or-COOH), basic group (for example: NH
2Or NHR
1, wherein, R=CH
3Or-CH
2-CH
3), halogen (Cl ,-Br ,-I ,-F) ,-OH ,-C ≡ CH ,-CH=CH
2, trimethylsilyl (Si (Me)
3), ferrocenyl or adamantyl (adamantine group), only list several examples.
In some instances, for example following compound is as insulating covering agent (capping agent): CH
3(CH
2)
nCH
2SH, CH
3O (CH
2CH
2O)
nCH
2SH, HSCH
2CH
2CH
2(SH) (CH
2)
nCH
3, CH
3(CH
2)
nCH
2NH
2, CH
3O (CH
2CH
2O)
nCH
2NH
2, P ((CH
2)
nCH
3)
3, O=P ((CH
2)
nCH
3)
3, wherein, n is the integer of 30 〉=n 〉=6.In other embodiments, n is the integer of 30 〉=n 〉=8.
In this, the example that should be pointed out that the covering reagent of the characteristic that provides more hydrophobic or hydrophobic substantially includes but not limited to: 1-sulfydryl-6-hexane phenyl acid (HS-(CH
2)
6-Ph), 1,16-dimercapto-n-Hexadecane (HS-(CH
2)
16-SH), 18-sulfydryl-stearylamine (HS-(CH
2)
18-NH
2), tri octyl phosphine or 6-sulfydryl-hexane (HS-(CH
2)
5-CH
3).
Provide the typical covering reagent of more hydrophobic or hydrophobic substantially characteristic to include but not limited to: 6-sulfydryl-caproic acid (HS-(CH
2)
6-COOH), 16-sulfydryl-palmitic acid (HS-(CH
2)
16-COOH), 18-sulfydryl-stearylamine (HS-(CH
2)
18-NH
2), 6-sulfydryl-hexylamine (HS-(CH
2)
6-NH
2) or 8-hydroxyl-spicy thioalcohol (HO-(CH
2)
8-SH).
Can use various host molecules, if this host molecule can and the complex compound that forms between (capped) that be capped nanocrystalline and described host molecule of described covering reagent react and giving with water-soluble.Usually, described host molecule is a water-soluble cpds, this water-soluble cpds contains the solvent that is exposed to polar group, and described polar group is oh group, carboxylate groups, sulfonate groups, phosphate group, amine groups, amide group group (carboxamide group) or the like for example.
The example of suitable host molecule includes but not limited to: carbohydrate (carbohydrate), ring polyamines (cyclic polyamine), cyclic peptide (cyclic peptide), crown ether, branch-shape polymer (dendrimer) or the like.
The example that can be used as the cyclic polyamine of host molecule for example comprises: four nitrogen heterocyclic ring molecules (teterazamacrocyclic molecules) and derivative thereof, four nitrogen heterocyclic ring molecules for example 1,4,8,11-tetraazacyclododecane tetradecane (being also referred to as cyclam), the derivative of four nitrogen heterocyclic ring molecules for example 1,4,7,11-tetraazacyclododecane tetradecane (isocyclam), 1-(2-aminomethyl)-1,4,8,11-tetraazacyclododecane tetradecane (scorpiand), 1,4,8,11-tetraazacyclododecane tetradecane-6, the 13-dicarboxylate, Sroczynski and Grzejdaziak are at J.Incl.Phenom.Macrocyclic Chem.35,251-260, in 1999 or Bernhardt etc. at J.Aus.Chem, 56,679-684 has described four nitrogen heterocyclic ring molecule and derivatives thereof in 2003; Six nitrogen heterocyclic ring complex compounds (hexaza macrocyclic complexes) (Hausmann, J. etc., Chemistry, AEuropean Journal, 2004,10,1716; Piotrowski, T. etc., Electroanalysis, 2000,12,1397); Or eight nitrogen heterocyclic ring compound (octaza macrocyclic compound) (Kobayashi, K. etc., J.Am.Chem.Soc.1992,114,1105).By Kobayashi, eight nitrogen heterocyclic ring compounds of descriptions such as K. also are (for example: an example of compound hydrophilic covering reagent) to be suitable for holding the polarity enclosed molecule above.Also can use and only in limited range, be water miscible cyclic polyamine, for example: 5,5,7,12,14, the 14-vegolysen, 4,8,11-tetraazacyclododecane tetradecane (Me6cylcam), and can (for example: carboxylate groups or sulfonate groups) substituting group is modified described cyclic polyamine with polar group is provided.Can be as other example of the big cyclammonium of host molecule for being recorded in Odashima, K., Journal ofInclusion phenomena and molecular recognition in chemistry, the compound in 1998,32,165.
The example of suitable calixarene comprises: Dondoni etc. are at Chem.Eur., J.3, and the 4-tertiary butyl-cup [4] aromatic hydrocarbons tetraacetic acid tetraethyl ester of describing in 1774,1997; Four semi-lactosi calixarene (tetragalactosylcalixarene) (Davis, AP. etc., Angew.Chem.Int.Edit., 1999,38,2979); Eight amino amides Resorcinol [4]-aromatic hydrocarbons (octaaminoamide resorcin[4]-arene) (Kazakov, E.K. etc., Eur.J.Org.Chem., 2004,3323); 4-sulfonic group cup [n]-aromatic hydrocarbons (Yang, W.Z., J.Pharm.Pharmacology, 2004,56,703); Sulfonation thia cup [4 or 6]-aromatic hydrocarbons (sulfonated thiacalix[4 or 6]-arene) (Kunsasgi-Mate S., Tetrahedron Letters, 2004,45,1387); Kobayashi etc. are at J.Am.Chem.Soc.116, in 6081,1994 and Yanagihara etc. at J.Am.Chem.Soc.114, the calixarene of describing in 10307,1992.
The example that can be used as the cyclic peptide of host molecule among the present invention includes but not limited to: Guo, W etc. are at Tetrahedron Letters, 2002,43,5665 or Peng Li etc. at Current Organic Chemistry, the calixarene of describing in 2002,6 with two diketopiperazines (dicyclodipeptide).
The crown ether that can be used as host molecule can have ring size arbitrarily, and for example: have the member ring systems that contains 8,9,10,12,14,15,16,18 or 20 atoms, the some of them atom is common heteroatoms, as O or S.The common crown ether of Shi Yonging includes but not limited to herein: water miscible 8-hat-4 compounds (wherein, 4 expression heteroatoms numbers), 9-hat-3 compounds, 12-crown-4-compound, 15-hat-5 compounds, 18-hat-6 compounds and 20-hat-8 compounds.The example of suitable described crown ether comprises (18-hat-6)-2,3,11,12 tetracarboxylic acids or 1,4,7, and 10-tetraazacyclododecanand-1,4,7,10 tetracarboxylic acids just list and give some instances.
In principle, various water-soluble branch-shape polymers all can provide the hydrophilic or hydrophobic cavity that can hold to the employed covering reagent of small part this paper (depending on that employed covering reagent is hydrophobic or hydrophilic).The suitable type of branch-shape polymer includes but not limited to: (for example: Boas and Heegard are at Chem.Soc.Rev.33 for polypropylen(e)imine branch-shape polymer, daiamid (polyamido amine) branch-shape polymer, polyarylether branch-shape polymer, poly-lysine (polylysine) branch-shape polymer, carbohydrate branch-shape polymer and silicon class branch-shape polymer (silicon dendrimer), 43-63 is summarized in 2004).
In an example, the described nanocrystalline carbohydrate that contains as host molecule.Such carbohydrate host molecule can for but be not limited to: oligose, starch or cyclodextrin molecular (referring to Davis and Wareham, Angew.Chem.Int.Edit.38,2979-2996,1999).
At some host molecules is in the example of oligose, and described oligose can contain 2-20 (for example: 6) monomeric unit on main chain.These oligopolymer can be straight chain or side chain.The example of suitable oligose includes but not limited to: 1, and 3-(dimethylene) benzene two bases-6,6 '-O-(2; 2 '-oxidation diethyl)-two-(2,3,4-three-O-ethanoyl-β-D-galactopyranoside (galactopyranoside); 1; 3-(dimethylene) benzene two bases-6,6 '-O-(2,2 '-oxidation diethyl)-two-(2; 3,4-three-O-methyl-β-D-galactopyranoside (Shizuma etc., J.Org.Chem.2002; 67; 4795); ring three-(1,2,3; 4; 5,6)-[α-D-glucopyranosyl-(1,2; 3; 4)-and α-D-glucopyranosyl] (Cescutti etc., Carbohydrate Research, 2000; 329; 647); ethynyl sugar (acetylenosaccharides) (Burli etc., Angew.Chem.Int.Edit.1997,36; 1852); or cyclic oligomer fructose (fructooligosaccharide) (Takai etc.; J.Chem.Soc.Chem.Commun., 1993,53).
If starch is as host molecule, then the molecular weight of starch can be about 1000-6000 dalton (Da).In some instances, the molecular weight of starch is about 4000Da 〉=Mw 〉=about 2000Da.Employed starch also can comprise amylose starch, for example: alpha-amylose or β-amylose starch.
Be suitable for comprising: alpha-cylodextrin, beta-cyclodextrin, γ-Huan Hujing, dimethyl-alpha-cylodextrin, trimethylammonium-alpha-cylodextrin, DM-, TM-, dimethyl-γ-Huan Hujing and trimethylammonium-γ-Huan Hujing as the example of the cyclodextrin of host molecule.
The method for preparing this type of water-solubility nanocrystalline is known in the art and for example is recorded among the WO2006/075974.In brief, these class methods comprise having the nanocrystalline of nanocrystal and to cover reagent react, thereby described covering reagent is connected on the surface of described nanocrystal, nanocrystalline and the host molecule that will obtain therefrom then contacts, thereby forms host-guest complex between described reagent and described water-soluble host molecule.Described (covering) reagent can be for hydrophilic or hydrophobic.If use purified metallic nano crystal or uniform ternary nanocrystals or quaternary nanocrystals, can carry out same reaction and prepare described nanocrystalline.Embodiment 3 provides the example for preparing this type of water-solubility nanocrystalline.
2, in another example, at least a nanocrystalline covering reagent that contains is connected nanocrystalline surface with this covering reagent and forms the first layer, and described covering reagent has at least one coupling group (coupling group).In addition, the polymkeric substance covalent coupling that forms the second layer and have at least one coupling group is at least one coupling group of described covering reagent.
In an example, described polymkeric substance contains at least one coupling part, and this coupling part reacts with the coupling group of described covering reagent, and the molecular formula of described polymkeric substance is:
Wherein, J is the coupling part that at least one coupling group with described covering reagent reacts, and m is at least 1 integer.
For this example is described, if for example described the first layer has amino-terminated group, the polymkeric substance that then forms the described second layer can have the amino covalence link coupled carboxyl that is used for described the first layer.In fact, be not that all can to participate in covalent coupling be possible for the coupling part (coupling moiety) of all existence and coupling group (coupling group).For example, 50% carboxyl can with the amino polymerization in the described the first layer
In another example, if described the first layer has the surface of carboxy blocking, then the second layer can have the amino with the carboxyl covalent coupling of described the first layer.Be not that all can to participate in covalent coupling also be possible for the coupling part of all existence and coupling group.For example, 50% amino can with the carboxyl polymerization in the described the first layer.
In another example, described polymkeric substance contains at least two coupling parts, and this coupling part reacts with at least one coupling group of described covering reagent.In this case, the molecular formula of described polymkeric substance is:
Wherein, J and K are the coupling parts, and described J and K are identical or different, and m and n are at least 1 integer.
Usually, if described covering reagent not only has the J end group but also have the K end group, then described polymkeric substance can have among a K and the J or not only have K but also have J, is used for and described covering reagent covalent coupling.For example, if described the first layer not only has the surface of carboxy blocking but also have amino-terminated surface, then described second layer polymkeric substance can only have in amino and the carboxyl or not only have amino but also have carboxyl, is respectively applied for carboxyl and amino covalence coupling with described the first layer.A part and described coupling group covalent coupling in the coupling part are just enough, and need not measure than there being described coupling part with exact chemical with respect to described coupling group.
In the another one example, described polymkeric substance contains at least three coupling parts, and described coupling part reacts with at least one coupling group of described covering reagent.In this example, the molecular formula of described polymkeric substance is:
Wherein, J, K and L are the coupling parts, and described J, K and L are identical or different, and m, n and p are at least 1 integer.In further embodiment, described polymkeric substance has the (NH of functional group different more than 3 or 3
2, COOH, NCO, CHO etc.), be used to provide water-soluble and with described the first layer link coupled surface.
The polymkeric substance that forms the described second layer will contact with nanocrystalline residing solvent.Therefore, in order to make nanocrystalline being dissolved in the described solvent (described solvent can contain water), for example, at least one among described coupling part J, K or the L preferably contains hydrophilic radical, and this hydrophilic radical is given water soluble shells with water-soluble.For this purpose, described polymkeric substance can also contain water-soluble at least one of giving water soluble shells had the part of hydrophilic radical.This part can be independent of described coupling part and exist or self just there is this part in described coupling part.
In an example, described coupling part J, K and L contain the functional group that is selected from amino, hydroxyl, carbonyl, carboxyl, itrile group, isocyanate group and halogen group separately.Obtain the polymkeric substance (homofunctional polymer) with functional group if desired, then the described coupling part of polymkeric substance can be made of for example hydroxyl, carboxyl or amino fully.In the case, described polymkeric substance is respectively polyvinyl alcohol, poly carboxylic acid and polyamine.
For obtain having different qualities (for example: the solvability in water) nanocrystalline, can use to have the polymkeric substance that surpasses a kind of monomeric other type.For example, can use Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, triblock copolymer or blended unregulated polymer as the polymkeric substance that is used to form the described second layer.Object lesson comprises: poly-(vinylformic acid-b-methyl methacrylate) segmented copolymer, poly-(methyl methacrylate-b-sodium acrylate) segmented copolymer, poly-(methacrylic tert-butyl acrylate-b-ethylene oxide) segmented copolymer, poly-(methyl methacrylate-b-sodium methacrylate) segmented copolymer and poly-(methyl methacrylate-b-N, N-DMAA) segmented copolymer.
Coupling part J in the polymkeric substance of above-mentioned molecular formula (III) can contain with described covering reagent in the various suitable functional group that reacts of coupling group.Hydrophilic segment K can contain the various functional groups that give the water-wet behavior of described polymkeric substance to give prominence to, and makes that thus described polymkeric substance is water miscible.The suitable example of described functional group comprises for example carboxylic group, amino group, oh group, amide group, ester group, anhydride group and aldehyde group.
In an example, described polymkeric substance is selected from the group of being made up of polyamine, poly-acetate (polyacetyl acid) or polyvalent alcohol (polyol).The scope of the molecular weight of described polymkeric substance can be from being lower than about 500 (about 400) to surpassing about 1000000.In one embodiment, the scope of described molecular weight can be about 600-1400000, and more preferably about 2000-750000.For using in the body, can select to be about 2000 lower limit, will the genotoxic potential of human body being minimized.
If the described covering reagent that uses contains the polymerisable unsaturated group as coupling group, then this unsaturated polymer can be used to form the second layer of described water soluble shells, and described unsaturated polymer comprises polyacetylene, poly-polyacrylic acid, polymine.
In another example, in order to obtain water-solubility nanocrystalline, at least one nanocrystalline containing:
Cover reagent, this covering reagent is connected on the described nanocrystalline surface, and to form the first layer, this covering reagent has at least two kinds of coupling group;
Low-molecular-weight coating reagent (coating reagent), this coating reagent form second layer and have at least two coupling parts with described coating reagent covalent coupling; And
At least one water soluble group, this water soluble group are used for giving the described second layer with water-soluble.
Described covering reagent can contain the end group that the surface of nanocrystal is had affinity.Described end group can include but not limited to: sulfydryl, amino, amine oxide (amine-oxide) and phosphino-.At least two coupling group of described covering reagent can be by hydrophobic region and spaced apart with described end group.Described at least two coupling group can contain the functional group that is independently selected from amino group, oh group, carbonyl group, carboxylic group, itrile group group, nitryl group, isocyanate group, epoxide group, anhydride group and halogen group separately.
Described covering reagent can contain two coupling group, and these two coupling group illustrate described covering reagent by hydrophobic region and spaced apart with described end group with following general formula:
In this molecular formula, X represents the end group that the surface to described nanocrystalline (or being known as nanocrystal sometimes) has affinity.X can be selected from S, N, P or O=P.The object lesson of Hn-X-part can comprise for example H-S-, O=P-and H
2Among the N-any one.Ra is the part that contains at least 2 backbone c atoms, and therefore has hydrophobic property.If Ra have outstanding hydrophobic property (for example: hydrocarbon), then Ra provide with Z part and described nanocrystal separate hydrophobic region.Y partly be selected from N, C ,-COO-or-CH
2O-.Z contains at least one coupling partly to be used for follow-up polymeric part, therefore gives the hydrophilic covering reagent of part with outstanding water-wet behavior.Typical polar functional group includes but not limited to :-OH ,-COOH ,-NH
2,-CHO ,-CONHR ,-CN ,-NCO ,-COR and halogen.Represent numeral with symbol k, n, n ' and m in the above-mentioned molecular formula.K is 0 or 1.Numeral n is the integer of 0-3 and the integer that n ' is 0-2; N and n ' be chosen as satisfy X and Y valence state demand separately.Numeral m is the integer of 1-3.Numeral k is 0 or 1.The condition that is suitable for is: when k is 0, Z will be attached on the Ra.The value of K=0 satisfies following situation: connection portion Z is directly connected on the Ra, and wherein, for example Ra is a circular part, as aliphatic cycloalkanes, aromatic hydrocarbon or heterocycle.But when k=1, Ra is a circular part, for example: be connected to the uncle's amino on phenyl ring or the cyclic hydrocarbon.In current molecular formula, Z is the functional group that is selected from the group of being made up of amino group, oh group, carbonyl group, carboxylic group, itrile group group, nitryl group, isocyanate groups, epoxide group, anhydride group and halogen group.Y or Z all can be used as coupling group.If Z occurs as coupling group, then Y can be with the structural constituent that connects coupling group Z (structural component).If there is no Z, then Y can form the part coupling group.
The Ra part can contain tens of to hundreds of backbone atoms in the above-mentioned molecular formula.In a specific embodiment, Ra and Z contain 2-50 backbone atoms independently of one another.Z can contain one or more amido linkages or ester bond.The suitable example that can be used as the Ra part comprises alkyl, thiazolinyl, alkoxyl group and aryl.
The term of Shi Yonging " alkyl " refers to side chain or non-side chain, straight chain or cyclic saturated hydrocarbyl herein, usually contain 2-50 carbon atom, for example: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, octyl group, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and cycloalkyl (for example: cyclopentyl, cyclohexyl).The term of Shi Yonging " thiazolinyl " refers to alkyl side chain or non-side chain herein, usually contain 2-50 carbon atom and contain at least one two key, usually contain 1-6 two key, more generally contain 1-2 two key, for example: vinyl, positive propenyl, n-butene base, octenyl, decene base, and cycloalkenyl group (for example: cyclopentenyl, cyclohexenyl).The term of Shi Yonging " alkoxyl group " refers to substituting group-O-R herein, and wherein R is alkyl as defined above.The term of Shi Yonging " aryl " unless otherwise defined, refers to contain the aromatic group of one or more aromatic rings herein.The aromatic ring of aryl is randomly replaced by one or more inert, non-hydrogen substituting group, and suitable substituents for example comprises: halogen, alkylhalide group (low alkyl group that preferred halogen replaces), alkyl (preferred low alkyl group), thiazolinyl (preferred low-grade alkenyl), alkynyl (preferred low-grade alkynyl), alkoxyl group (preferred lower alkoxy), carbalkoxy (preferred lower alkoxycarbonyl), carboxyl, nitro, cyano group and alkylsulfonyl.In all embodiments, Ra can comprise and contains heteroatoms () heteroaryl for example: nitrogen, oxygen or sulphur usually.
In some instances, Ra can include but not limited to: ethyl, propyl group, butyl and amyl group, cyclopentyl, cyclohexyl, ring octyl group, oxyethyl group, propoxy-, butoxy, benzyl, purine radicals, pyridyl, imidazolyl.
In another example, at least two coupling group of described covering reagent can be dual functional (homo-bifunctional) of the same race or xenogenesis dual functional (hetero-bifunctional), refer to that described covering reagent can contain at least two identical coupling group or two different coupling group respectively.Some illustrative example with suitable covering reagent of two or three coupling group have following structure respectively:
Described coating reagent wherein is that the typical covering reagent of xenogenesis difunctionality (that is, having 2 different coupling group) includes but not limited to:
In another example, described covering reagent and described coating reagent are by the coupling via various radical polymerization mechanisms of polymerisable unsaturated group, and described polymerisable unsaturated group is the two keys of C=C for example.This type of object lesson that covers reagent includes but not limited to: the end capped methyl methacrylate of ω-thiol, 2-butylene mercaptan, (E)-2-butylene-1-mercaptan, thioacetic acid S-(E)-2-butylene ester (S-(E)-2-butenylthioacetate), thioacetic acid S-3-methyl butene ester (S-3-methylbutenyl thioacetate), 2-quinoline thiomethyl alcohol (2-quinolinemethanethiol) and thioacetic acid S-2-quinoline methyl esters (S-2-quinolinemethyl thioacetate).
Second component that centers on the water soluble shells of nanocrystal is to form by the lower molecular weight coating reagent and the coupling of described covering reagent that will have water soluble group.Randomly, can use coupling agent, be present in coupling group in the described covering reagent with activation.Can add described coupling agent successively and have coupling coating reagent partly, add described coating reagent after promptly activation is finished; Perhaps, described coating reagent can add simultaneously with described coupling agent.
The determining of suitable coupling agents is in those skilled in the art's ken.An example of suitable coupling reagent is the 1-ethyl-3-[3-dimethyl aminopropyl that is used in combination with sulfo--N-hydroxy-succinamide (NHS)] carbodiimide (EDC).Also can use the coupling reagent of other type, include but not limited to: imide (imides) and pyrroles (azoles).Some examples of spendable imide class are: carbodiimide, succinimide and phthalimide (pthalimides).The tangible example of some of imide comprises: the 1-ethyl-3-[3-dimethyl aminopropyl that is used in combination with N-hydroxy-succinamide or other activated molecule] carbodiimide (EDC), sulfo--N-hydroxy-succinamide, N, N '-dicyclohexylcarbodiimide (DCC), N, N '-dicyclohexylcarbodiimide, N-(3-dimethyl aminopropyl)-N '-ethyl carbodiimide.
The described coating reagent that is used to form the second layer of described water soluble shells can contain one or more suitable coupling parts, and described coupling part can be reacted with the activatory coupling group on the described covering reagent.Usually, suitable coating reagent has at least 2 coupling parts, that is, in some instances, for example have 2,3 or 4 with described covering reagent in the functional group that reacts of activatory coupling group.When at least two couplings part of described coating reagent during with described covering reagent react, by for example forming ester bond or amido linkage with described coating reagent and described covering reagent covalent bonding (" crosslinked "), thereby form water soluble shells around described nanocrystal.
Be used to form the molecule that employed term " lower molecular weight coating reagent " in the second layer of described water soluble shells comprises non-polymeric (little).Depend on the type of the group that exists in this coating reagent molecule, the molecular weight of described coating reagent can be low or high.If described coating reagent has for example little side chain, the molecular weight of then described coating reagent can be lower.If when having huge side chain in the coating reagent, then should coat the molecular weight of reagent molecule with higher.Correspondingly, in some embodiments, be limited to about 200 dalton, about 400 dalton, about 600 dalton or about 1000 dalton on the molecular weight of described coating reagent.In other embodiment that uses the bigger covering reagent of high molecular or spatial volume, the described upper limit can be higher, for example is about 1200 dalton, about 1500 dalton or about 2000 dalton.According to this qualification, term " lower molecular weight coating reagent " also comprises oligomeric compound, and for example molecular weight is up to about 2000 daltonian oligomeric compounds.Term " coupling " and " covalent coupling " are often referred to two molecules are coupled together the various reactions that form an independent molecule, bigger entity (entity), for example: with acid and pure coupling formation ester, perhaps with acid and amine coupling formation acid amides.Correspondingly, can coupling be present in described covering reagent and coat described coupling group in the reagent and the various reactions of coupling part all fall in the intension scope of this term." coupling " also comprise make one or more unsaturated groups of in described covering reagent, existing as coupling group (for example: the two keys of-C=C-) with described coating reagent in corresponding coupling partial reaction, thereby by the free radical coupling that described coating reagent is covalently bound to described covering reagent layer.
Described covering reagent and coating reagent can have the functional group that reacts mutually separately, thereby implement polymerization.In an example, described coating reagent is the water soluble molecules that contains at least 2 couplings part, but each described coating reagent have at least one can with the functional group of the copolymerization of described coupling group reaction in the described covering reagent.In an example, described coating reagent has the water soluble molecules of following molecular formula:
Wherein,
T is used to regulate deliquescent part,
Rc is the part that contains at least 3 backbone c atoms,
G is selected from N or C,
Z ' but be the group of copolymerization,
N is 1 or 2 integer, and
N ' is 0 or 1, wherein, n ' is selected as to satisfy the valence state requirement of G.
Water soluble shells with characteristic of expection can partly have with Rc wherein and is lower than 30, preferably is lower than 20 or obtain more preferably less than the covering reagent of 12 backbone c atoms.One preferred embodiment in, Rc contains 3-12 backbone c atoms.Under specific experiment condition, when synthesizing nanocrystalline, this scope provides high coupling efficiency.T partly can be polarity/hydrophilic functional group, is used for regulating nanocrystalline solvability at this nanocrystalline residing environment.Correspondingly, group T can give described shell with water-wet behavior or hydrophobic property, thereby makes described nanocrystalline water-based environment and the non-aqueous environment of dissolving in.T can be selected from polar group, for example: hydroxyl, carboxyl, carbonyl, sulfonate groups, phosphate group, amino, carboxamide groups.In order to obtain being insoluble to the nanocrystalline of water-based environment, group T also can be for hydrophobic, for example: various aliphatic hydrocarbons or aromatic hydrocarbon (as, the derivative of lipid acid or benzene) or water-fast various other organic group.As T when being hydrophobic, after described coating reagent and the copolymerization of described covering reagent, can also modify by introducing hydrophilic radical.Group Z ' but be have can with the group of the copolymerization of the functional group of coupling part copolymerization on the described covering reagent.Suitable functional group for example includes but not limited to :-NH
2,-COOH or-OH ,-Br ,-C=C-.Z ' can contain aliphatic carbon chain or ring-type carbochain in addition, preferably has at least 2 backbone c atoms.
In an example, T can be derived from cyclodextrin molecular.Cyclodextrin molecular has great amount of hydroxy group, and these hydroxyls have improved the water-soluble of resulting multipolymer, and can also be attached at an easy rate on the biomolecules, is used for biomarker.The example of suitable cyclodextrin comprises: alpha-cylodextrin, beta-cyclodextrin, γ-Huan Hujing, dimethyl-alpha-cylodextrin, trimethylammonium-alpha-cylodextrin, DM-, TM-, dimethyl-γ-Huan Hujing and trimethylammonium-γ-Huan Hujing.
In another example, described coating reagent be selected from amino acid, the water soluble molecules of be preferably selected from diamino acid (diamino acid) or dicarboxylic acid amino acid (dicarboxylic amino acid).The object lesson of present forseeable diamino acid comprises: 2,4-diamino-butanoic, 2, and 3-diaminopropionic acid or 2, the 5-Ornithine only lists several examples.The dicarboxylic acid of the present invention's expection includes but not limited to aspartic acid and L-glutamic acid.
In other examples, described coating reagent is the water soluble molecules that is selected from the group of following composition:
Wherein, CD is a cyclodextrin, and
Contain in another example of unsaturated group (for example: C=C two keys) at described covering reagent, suitable coating reagent comprises diene and triolefin to be used for link coupled, for example: 1,4-divinyl, 1,5-pentadiene and 1,6-hexadiene.
The method for preparing a kind of (the 2nd) in the above-mentioned water-solubility nanocrystalline has for example been described in WO 2006/118543 and WO 2006/118542.Embodiment 4 and embodiment 5 have described some examples that prepare this type of water-soluble nanoparticles.
PCT/SG2008/000356 has described another selection that obtains water-solubility nanocrystalline.Be in amphiphilic polymer on this nanocrystal surface nanocrystalline the comprising by non-covalent or covalent interaction of describing in this application.
Described amphiphilic polymer can have following logical formula V:
In this general formula, m, o and p are selected from 0 to about 400 integer independently of one another, comprise: 1 to about 400 or about 2 to about 400 integer, for example: about 0 to about 400, about 0 to about 350, about 0 to about 300, about 3 to about 300, about 0 to about 250, about 0 to about 200, about 2 to about 200, about 0 to about 150, about 2 to about 150, about 0 to about 200, about 1 to about 200, about 3 to about 100, about 2 to about 100, about 0 to about 100, about 3 to about 50, about 2 to about 50, about 1 to about 50 or about 0 to about 50.As further instruction, in some instances, m can be selected from about 5 to about 50, for example: about 10 to about 45, comprise about 10 to about 43, and p for example can be selected from about 3 to about 40, for example: about 3 to about 35 or about 4 to about 30, and p for example can be selected from 0 to about 30, for example: 0 to about 25 or 0 to about 20.The summation of m+o+p is selected from about 10 to about 10000, comprise: about 10 to about 8000, about 10 to about 6000, about 10 to about 5000, about 10 to about 4000, about 10 to about 2000, about 10 to about 1000, about 10 to about 750, about 10 to about 600, about 10 to about 400, about 10 to about 250, about 10 to about 150, about 10 to about 100, about 15 to about 150, about 20 to about 150, about 15 to about 100 or about 20 to about 100.In some instances, m, o and p are selected from about 2 to about 300 integer independently of one another, comprise: about 3 to about 300, about 3 to about 250, about 3 to about 200, about 3 to about 150 or about 2 to about 200, about 3 to about 100, about 2 to about 100, about 3 to about 80, about 2 to about 80, about 3 to about 40 or about 2 to about 40 integer, and summation (m+o+p) is selected from from about 6 to about 400, comprising: about 10 to about 400, about 10 to about 350, about 10 to about 300, about 10 to about 250, about 10 to about 200, about 6 to about 200, about 10 to about 150, about 6 to about 150, about 10 to about 100, about 6 to about 100, about 10 to about 50 or about 6 to about 50.In one embodiment, summation (m+o+p) is 32.In another example, summation (m+o+p) is 48.The ratio of p/ (m+o) can be selected from 0 to about 25, for example: 0 to about 20,0 to about 15,0 to about 12,0 to about 10,0 to about 8,0 to about 6, to about 4, to about 3 or to about 2.In an example, the ratio of p/ (m+o) is about 1.
R
2Be above-mentioned first aliphatic group, main chain have about 3 to about 20 carbon atoms and 0 to about 3 heteroatomss.Described heteroatoms is selected from the group of N, O, S, Se and Si.R
3Be above-mentioned second aliphatic group, main chain have about 3 to about 80 carbon atoms and 0 to about 40 heteroatomss.Described heteroatoms is selected from N and O.The described second aliphatic group R
3But group with copolymerization.Be understandable that outside arranging divided by the form of block, the separate unit shown in the above-mentioned formula (individual unit) can be arranged in various orders (comprising random).Therefore, above-mentioned general formula has only defined and has had the m unit in the described polymkeric substance:
The o unit:
With the p unit:
Can prepare amphiphilic polymer by the method for describing among the PCT/SG2008/000356.It is essentially no at least usually crosslinked that this states amphiphilic polymer.Correspondingly, in described amphiphilic polymer, the described second aliphatic group R
3But the group (the preceding) of copolymerization can be used for various crosslinked or copolymerizations.
For example, in this type of nanocrystalline method that preparation coats with described amphiphilic polymer, the maleic anhydride polymkeric substance forms hydrophilic skeleton as reactant on described amphiphilic polymers.Described maleic anhydride polymkeric substance can be that Chemical Abstract (chemical abstracts) registration number that is available commercially is poly-(iso-butylene-alt-maleic anhydride) alternating copolymer of 26426-80-2, is also referred to as iso-butylene-copolymer-maleic anhydride.Obtainable other commodity are called BM 30AE20, Fibersorb
TMSA 7200H, IB 6, KI Gel and
Can also from for example Sigma-Aldrich (St.Louis, MO, USA) or SinoChemexperCompany (Shanghai PRC) obtains.Described maleic anhydride polymkeric substance also can be that the ChemicalAbstract registration number is poly-(ethene-alt-maleic anhydride) alternating copolymer of 106973-21-1, is also referred to as ethene-maleic anhydride alternate copolymer.This maleic anhydride polymkeric substance can (Bayonne, NJ), article number be 27109P, and commodity are by name available from for example Rutherford Chemicals
Or
E 60.In above-mentioned formula V, n can be about 10 to about 10000 arbitrary integer, and for example: about 10 to about 5000, about 10 to about 2000, about 10 to about 1000, about 20 to about 1000, about 10 to about 800, about 20 to about 800, according to appointment 10 to about 400.In an example, n is 32.The above-mentioned example of maleic anhydride polymkeric substance should not be understood that it is determinate, but any obtainable maleic anhydride polymkeric substance (also comprise and need synthetic maleic anhydride polymkeric substance) particularly can all be suitable for according to the maleic anhydride polymkeric substance of conventional steps preparation known in the art.For example, the various maleic anhydride polymkeric substance that prepare according to the step of describing in United States Patent (USP) 3846383 and 6316554.At Frank, H.P. has summarized the employed conventional steps in this area in the summary of Makromolekulare Chemie (1968) 114,113-121, and this conventional steps relate to superoxide for example under existing maleic anhydride and the radical copolymerization of alkene.
Monofunctional compound and dual functional at least compound are as further reactant.In treating processes, described monofunctional compound changes the above-mentioned first aliphatic group R into
2The functional group of described monofunctional compound can with acid anhydride Cheng Jian.Described dual functional at least compound changes the described second aliphatic group R into
3(the preceding).Described dual functional at least compound can have two, three, four or more functional group.In the described functional group one can with acid anhydride Cheng Jian.The functional group of other of described dual functional at least compound is copolymerizable.The part of anhydro ring and the reaction of described monofunctional compound cause the formation of hydrophobic side chain, and this hydrophobic side chain can interact with the hydrophobic surface of nanoparticle described herein.Another part of described anhydro ring is used for described dual functional at least compound is connected to skeleton.Be used for amount with the nucleophilic reagent of polyanhydride chain reaction by change, can control the relative populations of hydrophobic units on the polymer backbone and carboxyl.Therefore, described monofunctional compound of the present invention can with available anhydro ring at least about 25%, for example at least about 35%, at least about 50%, at least about 70% or at least about 75% reaction.Described dual functional at least compound of the present invention can with available anhydro ring at least about 5%, for example at least about 8%, at least about 10%, at least about 15%, at least about 20% or at least about 25% reaction.
The functional group of described monofunctional compound can be selected from but be not limited to: amino group, oh group, thiol group, selenium oh group (selenol group), halogen group, ether group, sulfide group or the like.The carbon atom of the alkyl chain of described monofunctional compound is about 2 to about 20, for example: about 3 to about 20, comprise about 5 to about 20, about 5 to about 15, about 7 to about 20, as 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20.Further, described monofunctional compound has 0 to about 2 heteroatomss, for example: 1 heteroatoms.Described heteroatoms for example can be N, O, S, Se or Si.The example of monofunctional compound can be but be not limited to: alkylamine, wherein the definition of alkyl as above.In one embodiment, described alkylamine can be Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, n-octyl amine or n-dodecane amine.
Usually, described bifunctional at least has two or more different functional groups.Can select any functional group as in the described bifunctional at least any one, (usually only one) can become key with acid anhydride as long as in the described bifunctional at least one.Can be selected from first group of maleic anhydride radical reaction but be not limited to: amino group, oh group, thiol group, selenium oh group, halogen group, ether group, sulfide group or the like.But second functional group with the maleic anhydride radical reaction can not be the group of copolymerization.But copolymerization refer to this group can with other functional group's polymerization.But the example of the group of suitable copolymerization includes but not limited to: amino, hydroxyl, glycidyl allyl ether base, epoxy group(ing), oxetanyl and C=C key are (for example: allyl group).
The alkyl chain of described difunctional compound at least has about 3 to about 80 carbon atoms, comprise: about 3 to about 70 carbon atoms, about 3 to about 60 carbon atoms, about 3 to about 40 carbon atoms, about 10 to about 80 carbon atoms, about 10 to about 60 carbon atoms, about 25 to about 60 carbon atoms, about 10 to about 40 carbon atoms, about 3 to about 20 carbon atoms or about 3 to about 10 carbon atoms, for example 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43 or 44 carbon atoms.Further, described dual functional at least compound has 0 to about 45 heteroatomss, comprise: 0 to about 40 heteroatomss, 1 to about 40 heteroatomss, about 2 to about 40 heteroatomss, about 2 to about 30 heteroatomss or about 0 to about 3 heteroatomss, 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42 or 43 heteroatoms for example, described heteroatoms is N or O for example.
In the process that forms above-mentioned amphiphilic polymer, the reaction between the maleic anhydride polymkeric substance of formula V (aforementioned), described monofunctional compound and the described dual functional at least compound can be carried out in the presence of alkali.Usually, can use the alkali that is suitable for intended purposes arbitrarily.In one embodiment, described alkali is nucleophilic alkali.Nucleophilic alkali is the alkali with alkalescence and nucleophilicity.Exemplary example includes but not limited to: diisopropyl amide lithium, tetramethyl piperidine lithium, diisopropylethylamine (H ü nig ' s alkali), 1,5-diazabicylo [4.3.0]-ninth of the ten Heavenly Stems-5-alkene, 1,8-diazabicylo [5.4.0]-11 carbon-7-alkene, two (trimethyl silyl) acid amides, hexamethyldisilane (hexamethyldisilazane) or phorone magnesium (bismesitylmagnesium).
In the process that forms amphiphilic polymer, the reaction of the anhydride group of described maleic anhydride polymkeric substance forms amide group or ester group usually, thereby nonpolar side chain is provided.This side chain comprises the part that is formed by described monofunctional compound, and for example: alkyl chain and at least one heteroatoms, this heteroatoms are the individual atoms in described ester group or the amide group, and the part that is formed by described monofunctional compound links to each other with this heteroatoms.Therefore described first aliphatic portion comprises part and group COO-, CO-NH-or the CO-N-that is formed by described monofunctional compound.In embodiment, when described group is CO-N-, form secondary amide, therefore described first aliphatic portion comprises 2 parts that formed by described monofunctional compound.
It should be noted that in this respect that in forming the example of secondary amide described first aliphatic portion also can contain part being formed by described monofunctional compound and by a part of described dual functional at least compound formation.For clear, comprise by all being understood that second aliphatic portion to the described any aliphatic portion that lacks the part of dual functional compound formation.Correspondingly, not only comprised the part that forms by described monofunctional compound but also comprised that aliphatic portion by the part of described dual functional at least compound formation should be understood that second aliphatic portion of branching.
Further, each anhydride group of described maleic anhydride polymkeric substance all can react (face as follows) with one or two monofunctional compound or with one or two dual functional at least compound.Usually, no matter be monofunctional compound or dual functional at least compound, a kind of reagent react of anhydride group and quantity maximum.The result has formed hydroxy-acid group, and this hydroxy-acid group provides negative charge usually in solution.In addition, many anhydride groups do not react.These anhydride groups are hydrolyzed in treating processes of the present invention usually, and therefore hydroxy-acid group further is provided.The method that it will be appreciated by persons skilled in the art that formation amphiphilic polymer of the present invention does not need to use for example any coupling agent of linking agent.
Before pointed out to gather (iso-butylene-alt-maleic anhydride) alternating copolymer and can react (the summary of Japanese patent application JP 57016004 with fatty amine, Fernandez-Arguelles, M.T. etc., NanoLetters (2008) 7,9,2613-2617), have been found that in addition two-, three-and higher functionalized compound can be as the addition reaction thing in the one kettle way synthetic (one-pot synthesis).Usually can so that described two-or the mode that higher functionalized compound is only participated in a reaction control reaction conditions, only on the hydrocarbon skeleton of described polymkeric substance, form a key thus.Described two-or all the other functional groups of higher functionalized compound can be used for coupling and crosslinking reaction subsequently.In this respect, it should be noted, the hydrocarbon skeleton of described amphiphilic polymer can have the polarity side group and have the side chain of alkyl chain, described alkyl chain have about 3 to about 80 carbon atoms and 0 to about 40 heteroatomss that are selected from N and O, but described side chain has the group of copolymerization.As mentioned above, but the group of described copolymerization can be amino, hydroxyl or the group that contains end or interior C=C or C ≡ C key (for example: end-CH=CH
2Base, end-C ≡ CH base, interior-CH=CH-base or interior-C ≡ C-yl).As mentioned above, but the group of described copolymerization also can comprise end or interior C=C or C ≡ C key and other functional group or vicinal (vicinal) heteroatoms or geminal (geminal) heteroatoms, for example: formula-G-CH=CH-or G-C ≡ C-, wherein G be N, O or-the CH=CH-group or-C ≡ C-group.
Described polymerisable group can be identical or different with all the other groups of described dual functional at least compound.In the identical example of described functional group, can those should not covered with the functional group of described maleic anhydride polymer reaction, participate in the polymerization process to prevent these functional groups.A large amount of protecting groups well known to those skilled in the art can be used for various functional groups.As an exemplary example, hydroxyl can be protected by isopropylidene.Can remove this type of protecting group after polymerization, therefore no longer protected described functional group can be used for coupling, crosslinked or copolymerization.For example, the isopropylidene protecting group of protection hydroxyl can be removed by acid treatment.What those skilled in the art will further recognize is in the synthetic process of independent dual functional at least compound, can introduce described protecting group in advance.
PCT/SG2008/000356 has described the nanocrystalline example for preparing described amphiphilic polymer and be coated with described amphiphilic polymer.Embodiment 6 has also listed some examples.Can be used for nanocrystalline Fernandez-Arg ü elles, M.T., the Yakovlev of for example being recorded in of other amphiphilic of the present invention, A. the article that waits (2007, Nano Lett., the 7th the volume, the 9th phase, the 2613rd page) and Cheng-An, J.L., Ralph, A. the article that waits (2008, small, the 4th the volume, the 3rd phase, the 334th page) in.Cheng-An, J.L., Ralph, the amphiphilic that A. etc. describe is nanocrystalline based on poly-(maleic anhydride) skeleton.The part of anhydro ring and the reaction of alkylamine cause the formation of hydrophobic side chain, and this hydrophobic side chain is used to insert the hydrophobic surfactant layer of nano grain surface.Another part of described anhydro ring is used for functional organic molecule is connected to described skeleton.Fernandez-Arg ü elles, M.T., Yakovlev, A. wait the nanocrystalline amphiphilic polymer of describing that contains of amphiphilic, this amphiphilic polymer is by under the reaction conditions of the anhydro ring of described polymer backbone, is connected to polarity skeleton (poly-(iso-butylene-alt-maleic anhydride) alternating copolymer) by the hydrophobic hydrocarbon chain (n-Laurylamine) with aminofunctional and goes up and synthetic.
In addition, Dubertret etc. (Science (2002) 298,1759) have also described water-solubility nanocrystalline.Dubertret and his colleague are encapsulated in the micellar hydrophobic core nanocrystalline; described micella be 40% 1; 2-two palmitoyl-sn-glycerol-3-phosphate thanomin-N-[methoxyl group (polyoxyethylene glycol)-2000] and 60% 1, the mixture of 2-two palmitoyl-sn-glycerine-3-phosphocholine.Described micella provides hydrophobic interfaces and keeps high colloidal stability for nano particle.The existence of PEG layer is the described nanocrystalline prerequisite of solubilising.
Other author has reported the formation that does not rely on as the polymer micelle in Dubertret and his colleague's the method, but directly uses the feasibility of amphiphilic polymer clad nano crystalline substance.The low-molecular-weight polyacrylic acid of amphipathic, alkyl-modified (octylame or Isopropylamine) be successfully used to coat the nanocrystalline of TOPO protection and make nanocrystalline soluble in water (Nat.Biotechnol. (2003) 21 for Wu, X. etc., 41; Mattheakis, L.C. etc., Anal.Biochem. (2004) 327, and 200; Luccardini C. etc., Langmuir (2006) 22, and 2304).In a research, Luccardini etc. (ditto) have reported the interaction of the nanocrystalline pH dependence that coats with lipid film.They find: in biological buffer, the interaction between the nanocrystalline and described film of polymer overmold can be controlled by the pH of damping fluid.In the work of Gao etc., high-molecular weight amphiphilic ABC triblock copolymer is made of butyl polyacrylate part (hydrophobic), polyethyl acrylate part (hydrophobic) and polymethyl acid moieties (hydrophilic), this high-molecular weight amphiphilic ABC triblock copolymer is used for directly sealing quantum dot (QD) (Gao X. etc., Nat.Biotechnol. (2004) 22,969).
Be used for the another kind of polymkeric substance that hydrophobicity QD directly transfers to water be poly-(maleic anhydride-alt-1-tetradecene) alternating copolymer (Nano Lett. (2004) 4 for Pellegrino, T etc., 703; Yu, W.W. etc., J.Am.Chem.Soc. (2007) 129, and 2871).Two by adding (the amino hexyl of 6-) amine crosslinker improves the stability of polymer shell.
Except that described nanocrystalline, plant of the present invention can also contain organic dye, for example: fluorophore.The example of fluorophore includes but not limited to: Hydroxycoumarin (blueness), for example umbelliferone-3-carboxylic acid; Methoxy coumarin (blueness), for example ayapanin-4-acetate; Cyanine dyes, for example spend cyanines (Cy2, deep green (green dark)), indoles carbon cyanines (Indocarbocyanine) (Cy3), indoles two carbon cyanines (Indodicarbocyanine) (Cy5); Aminocoumarin (blueness), for example 7-aminocoumarin; FAM (deep green), for example 5-Fluoresceincarboxylic acid (5-FAM); Alexa Fluor, for example Alexa Fluor 350,405,430,488,500,514,532,546,555,568,594,610,633,647,660,680,700 and 750; Fluorescent yellow (FITC; CAS registration number: 2321-07-5) (light green); HEX fluorophore (light green), 6-carboxyl-2 ' for example, 4,4 ', 5 ', 7,7 '-chlordene fluorescein; TRITC (yellow), for example: tetramethyl phosphonium chloride rhodamine 6-isothiocyanic acid (Tetramethylrhodamine6-isothiocyanate chloride) is (6-TRITC); R-phycoerythrobilin (PE) (yellow); Texas red (Texas Red) (C
31H
29S
2N
2O
6Cl1; CAS No.:82354-19-6) (orange); Carboxyl tetramethyl-rhodamine (TAMARA) (redness); 6-carboxyl-X-rhodamine (6-Rox) (redness); Or allophycocyanin (A-PC) (redness), only list some examples.In an example, with fluorescein as fluorophore, described fluorescein can with the nanocrystalline (see figure 4) of mixing.
Organic dye can also include but not limited to chromophore, for example: azo-compound, Lyeopene, β-Hu Luobusu, cyanin, fluorescent yellow and fluorescein.
Nanocrystalline and this type of mixture organic dye can produce the plant of different colours, and this plant contains the mixture of at least a nanocrystalline and at least a organic dye.
On the other hand, the present invention relates to nanocrystalline plant be carried out painted method with at least a, this method comprises:
A kind of solution is provided, and this solution contains at least a nanocrystalline in this solution of being dissolved in;
Described plant is contacted with described solution.
In aforesaid method of the present invention, nanocrystalline in the mixture that is in suitable solvent or described solvent at first is provided, that is, described solution is solvent and at least a nanocrystalline mixture, wherein, described nanocrystalline being dissolved in the described solvent.
In the nanocrystalline solvent that should be dissolved in separately of suitable finger in this regard.The example of this kind solvent for but be not limited to aprotic solvent and/or non-polar solvent, for example: non-proton non-polar solvent.Described non-polar solvent can include but not limited to: mineral oil, hexane, heptane, hexanaphthene, benzene, toluene, pyridine, methylene dichloride, chloroform, tetracol phenixin, dithiocarbonic anhydride, dioxane, ether, 1-octadecylene, 9-octadecylene, diisopropyl ether, ethylene glycol monobutyl ether, tetrahydrofuran (THF) or their mixture.In an example, the 1-octadecylene is used to dissolve described nanocrystalline.
In another example, use protonic solvent.Protonic solvent is to have the solvent that for example is connected to the hydrogen atom of (in amino) on (in hydroxyl) on the Sauerstoffatom or the nitrogen-atoms.More loosely say, anyly contain dissociable H
+Molecular solvent (for example: hydrogen fluoride) all be known as protonic solvent.The molecule of this kind solvent can provide H
+(proton).The example of polar aprotic solvent includes but not limited to: water, methyl alcohol, ethanol, butanols, the trimethyl carbinol, phenol, hexalin, formic acid, acetate, dimethyl-arsinic acid [(CH
3)
2AsO (OH)], aniline, N, dinethylformamide, N, N-diisopropylethylamine or chlorophenol.Especially, when using water-solubility nanocrystalline, can use protonic solvent, for example water.
Other example of suitable non-polar solvent is non-polar.Nonpolar ion liquid example includes but not limited to: two (trifyl) acid amides of two [(trifluoromethyl) alkylsulfonyl] acid amides of 1-ethyl-3-Methylimidazole; two [(trifluoromethyl) alkylsulfonyl] the acid amides trifluoroacetates of 1-ethyl-3-Methylimidazole; 1-butyl-3-Methylimidazole hexafluorophosphate; two (trifluoromethyl sulfonyl) imide of 1-hexyl-3-Methylimidazole; two (trifluoromethyl sulfonyl) imides of 1-butyl-3-Methylimidazole; three hexyls (two [oxalate (2-)] borates of tetradecyl) Phosphonium; 1-hexyl-3-Methylimidazole three (pentafluoroethyl group) three fluorophosphates; 1-butyl-3-methyl-imidazoles hexafluorophosphate; three (pentafluoroethyl groups), three fluorophosphates; three hexyls-(tetradecyl) Phosphonium; N "-ethyl-N; N; N ', N '-tetramethyl-guanidinesalt; 1-butyl-1-crassitude three (pentafluoroethyl group) three fluorophosphates; two (trifluoromethyl sulfonyl) imides of 1-butyl-1-crassitude; 1-butyl-3-Methylimidazole hexafluorophosphate; two (trifluoromethyl sulfonyl) imides of 1-ethyl-3-Methylimidazole and 1-normal-butyl-3-Methylimidazole.The example of polar aprotic solvent includes but not limited to: butanone, methyl iso-butyl ketone (MIBK), acetone, pimelinketone, ethyl acetate, isobutyl isobutyrate, glycol diacetate, dimethyl formamide, acetonitrile, N,N-dimethylacetamide, Nitromethane 99Min., acetonitrile, N-Methyl pyrrolidone and dimethyl sulfoxide (DMSO).
In an example, described solvent is a high boiling solvent.The example of this kind solvent comprises 1-octadecylene or 9-octadecylene.Their boiling point is higher than 250 ℃.Other example includes but not limited to: dowtherm A (Dowtherm A), dowtherm A are two kinds of highly stable compound (biphenyl (C
12H
10) and phenyl ether (C
12H
10O)) eutectic mixture, boiling point are 275.1 ℃; Perhaps general formula is C
12H
10-xCl
xPolychlorobiphenyl, for example boiling point is 359 ℃ Therminol 66.In another embodiment, can use low boiling point solvent, described low boiling point solvent is hexane, hexanaphthene, chloroform or the like for example.
Water-solubility nanocrystalline can be mixed at an easy rate or water-soluble solution in.This aqueous solution is suitable for by root or cuts stem (cut stem) by plant absorbing.When using water-insoluble (that is, hydrophobicity) nanocrystalline, need this nanocrystalline being dissolved in is suitable for by root or cuts stem by in the solvent of plant absorbing, for example: hydrophobic solvent or amphoteric solvent.Except that the octadecylene that in an embodiment described herein (seeing embodiment 1), uses, also can use other hydrophobic solvent.Example comprises vegetables oil, for example: soybean oil (soyoil), rapeseed oil (rape oil), sunflower seed oil, sweet oil, only for some examples.Described hydrophobic nano crystalline substance is by root or cut stem and can be dissolved in earlier in this class oil before by plant absorbing.
Also the hydrophobic nano particle can be scattered in the non-hydrophobic solvent.For example, by the hydrophobic nano crystalline substance being dispersed in aforesaid polar solvent or aqueous solvent can prepare water-fat liquor.
In another aspect of this invention, the root of plant is dipped in the described solution.On the other hand, the stem of plant is cut and has the above-mentioned plant that cuts stem place described solution.In the case, because plant cell wall and skin material are to be made of a large amount of longer chain fatty acids, therefore with emanative nanocrystalline being scattered in the long chain hydrocarbon, for example: 1-octadecylene or 9-octadecylene, only enumerate above-mentioned two examples.
In an example, a kind of orchid of spending the stem of noble dendrobium in vain by name is used for absorbing and is dissolved in the nanocrystalline of octadecylene.When lacking the transhipment passage that is specifically designed to organic medium in the plant, nanocrystallinely be diffused in the flower with low-down speed.Fig. 2 shows by the stem immersion of cutting with plant and contains an example giving plant dyeing in the nanocrystalline organic solvent.In another example, be dissolved in a kind of organic dye with mixture fluorophore nanocrystalline.Then, the stem of cutting of plant is immersed in this solution, after by this plant absorbing, this plant demonstrates multiple color and (for example sees Fig. 4 a).
Many in another aspect of this invention, gas first portion of plant or whole strain plant contact with the solution that contains the mixture that is dissolved at least a nanocrystalline or the nanocrystalline and organic dye in the suitable solvent.
On the gas first portion of plant or whole strain plant, described plant is contacted by dipping or with described spray solution with this solution.Fig. 1 has shown an example of spending the orchid of the stem of noble dendrobium in vain by name, and this orchid dip-coating has described solution.Described mixture nanocrystalline or nanocrystalline and organic dye is absorbed by the surface of plant, and part is also absorbed by epidermis/cuticular vegetable cell.
Described at least a nanocrystalline concentration is about 0.001-1mmol/L, perhaps is about 0.01-1mmol/L, perhaps is about 0.1-0.5mmol/L.The concentration range of spendable organic dye is 0.001-1.0mol/L, perhaps is about 0.01-1mmol/L, perhaps is about 0.1-0.5mmol/L.
When being exposed to the light of specific wavelength, plant of the present invention can present by by take at least a nanocrystalline or with at least a nanocrystalline color of giving that contacts.This can take place under visible spectrum and UV light.Most ofly nanocrystallinely send specific color being exposed to the UV light time.
Also can suitably put into practice the present invention that this paper exemplarily describes lacking this paper and do not have under the condition of concrete disclosed any element or multiple element, a kind of qualification or multiple qualification.Therefore, for example, term " comprises ", " comprising ", " containing " or the like should be understood that open but not enclosed.In addition, term used herein and phraseology are used as illustrative term but not are determinate, and when using this type of term and phraseology, be not the purpose of any Equivalent of the feature that illustrates and describe for eliminating or part, but be understandable that various modifications fall in the claim scope of the present invention.Therefore, should be understood that, although by preferred embodiment and optional feature the present invention has been described particularly, those skilled in the art can make amendment and conversion to the concrete disclosed the present invention of this paper, and this type of is revised and conversion all falls within the scope of the present invention.
This paper is from broadly and prevailingly having described the present invention.The kind and the subgenus group that fall into each narrow sense in the above-mentioned general scope of disclosure also are parts of the present invention.This comprises that limiting the generality of the present invention of getting rid of any theme from described genus with a collateral condition or negativity describes, and whether the material of no matter getting rid of specifies herein.
Other embodiment falls into following claims and non-restrictive example.In addition, when feature of the present invention or aspect are described with the Ma Kushi group, it will be understood by those skilled in the art that the present invention also can with this Ma Kushi group any one independently member or member's subclass be described.
Embodiment
1.1 it is nanocrystalline that surface adsorption/absorption absorbs emissivity
The multiple method that the color of flower (flora) and leaf (foliage) is modified is arranged.Compare with genetic modification, because technology is easy, so physical method is more attractive.By the nanocrystalline surface adsorption/absorption of emissivity is carried out in orchid (for example: spend the stem of noble dendrobium in vain) dip-coating in the nanocrystalline solution of CdZnSe, this orchid excites 302/345nm to excite the flower (Fig. 1) that shows high emission down at UV.
It is nanocrystalline that root is taken in the emissivity that is in the octadecylene
Because cell walls and the skin material of plant mainly are made of longer chain fatty acid, so we have designed and are scattered in long chain hydrocarbon (for example: the emissivity octadecylene) is nanocrystalline.Then, spend dendrobium in vain and take in the identical CdZnSe nanocrystalline (quantum dot) that is dissolved in the octadecylene.Special when being used for the transhipment passage of organic medium when lacking, quantum dot is diffused in the flower with extremely slow speed.Under UV excites, have the abundant absorption of the minimum 1 hour absorption of the luminous needs of visible and then need 3 hours.Compare with the diffusion of veiny (vein-like) fluorescent yellow, observe nanocrystalline periphery (periphery) and be ingested with higher speed along sepal.Then, begin diffusion in weak (less) directed mode from the edge of mediad petal and sepal.This can with octadecylene with the explaining of the chemical compatibility of the stratum corneum (cuticular) of plant and cell walls height.15 hours absorption makes whole flower all develop the color (Fig. 2, the picture of below).
Usually, can say so also that (for example: the absorption time mixture of different types of nanocrystalline or other organic dye or nanocrystalline and organic dye) can be controlled the dyeing of plant by changing staining agent.In an example, can use the mixture of the nanocrystalline and fluorescent yellow of CdZnSe.To the solution that contains two kinds of staining agents carry out the absorption of short period of time can be so that vein be dyeed by fluorescent yellow flower and sepal ovary zone, base portion and peripherally dyeed by CdZnSe is nanocrystalline.
Root is taken in emissivity quantum dot and dyestuff successively
Next explanation is dissolved in the absorption successively of the nanocrystalline and fluorescent yellow dye aqueous solution of CdZnSe in the octadecylene.Taking in nanocrystalline and organic dye successively can obtain multicolour and modify.By cutting stem, then fluorescent yellow is taken in (also by cutting stem) in the flower by 15 minutes absorption to the nanocrystalline absorption of carrying out 4 hours.To be ovary zone be the emission of uniting of fluorescent yellow-nanocrystalline to the result, this fluorescent yellow-nanocrystalline emission of uniting is expanded into the distinct emission opposite with petal and sepal, and is (minimum although the light field form (brightfield appearance) that Fig. 4 a) spends changes.
Under confocal microscope, observe cross section (Fig. 4 b) corresponding to the stem of above-mentioned absorption.Except that the standard confocal imaging, confocal light spectrum image-forming (spectral confocal image) is used to confirm the existence of CdZnSe nanocrystalline (quantum dot) and fluorescent yellow.By select suitable wavelengths, the increment and minimize autofluorescence of sampling, guaranteeing does not have crosstalk information, then confocal images is pure on spectrum.
Dyestuff and nanocrystalline specificity absorption on cell walls on the vertical section of stem, have further been studied.Consistently, observe clearly water base zone (water-based region) and observe hydrophobic region along vascular bundle around above-mentioned vascular bundle.Fluorescent yellow and nanocrystalline emission data have been compared in the spectroscopic analysis of the different zones in cross section.Based on above-mentioned dyestuff and nanocrystalline emission behavior, use confocal software on numeral, the expansible fragment to be reconstructed into corresponding hydrophobic cell signal and hydrophilic cell signal.
The white stem of noble dendrobium that use is purchased carries out dyestuff and nanocrystalline absorption.Stem cut and immerse this stem in the nanocrystalline 1-octadecylene solution of the CdZnSe of 0.001-1.0mmol/L (or be 0.03mol/L in this specific examples) or in uranine (Fluka 46960) aqueous solution of 0.001-1.0mmol/L (or being 0.03mol/L in this specific examples).If wish whole strain plant the visible color is arranged all, described stem was flooded about 4 hours in containing the nanocrystalline solution of CdZnSe, in containing the solution of fluorescent yellow, flooded 15 minutes then.Then, before drying, respectively with octadecylene or the described stem of water washing with the KimWipes toilet paper.Then with the image under the digital camera Cybershot DSC-T1 of the Sony shooting UV.
Carefully the section of stem section is used for confocal imaging with surgical knife.Then each stem section section is transferred on the microscope glass cover glass carefully.Use is equipped with the sample imaging of Nikon Clsi laser scanning confocal microscope to placing towards object lens of non-blended light spectrum image-forming and fluorescent probe.
It is nanocrystalline to prepare CdZnSe with following method
Thereby use liquid oleic acid and the liquid octadecylene prepares luminous or magnetic Nano brilliant make nanocrystalline.As an example, below provided the step of preparation luminescence nanocrystalline: 1.0mmol Cadmium oxide, 0.5mmol zinc oxide, 3.1mmol selenium are added in the flask that contains 3.1mmol oleic acid and 10mL octadecylene, follow then to stir to outgas and be heated to 300 ℃, up to forming clear soln.Reaction is proceeded 30 minutes, and reactant naturally cools to room temperature.The nanocrystalline absorption that is directly used in flower that obtains.
Also can use soybean oil to replace oleic acid.As described in epimere or top embodiment 1, can in these media, form nanocrystalline.Also can be to after carrying out purifying by other method preparation nanocrystalline, with nanocrystalline being distributed in the solution that makes.
2. use lower boiling non-polar solvent synthetic binary metal oxide in uniform mixture
2.1 synthetic binary metal oxide ZnO
Under 260 ℃, the ZnO of 3.0mmol is dissolved in the oleic acid of 7.5mmol, to form clear soln.After being cooled to room temperature, add 18mL hexane and 6mmol oleyl amine, then this solution is transferred in the Parr reactor 4950 of 100mL and used N
2Gas purges.Under agitation mixture is heated to 320 ℃ and under this temperature, kept 30 minutes rapidly.Then, by removing heating and cooling simply reaction is stopped.Come the final product of purifying by easy centrifugal dispersion steps, promptly can collecting precipitation nanocrystalline also carries out drying or (for example: be used for hexane) storing is dissolved in organic solvent again.
2.2 synthesis of ternary quantum dot ZnCdSe
Under 320 ℃, the ZnO of 0.3mmol and the CdO of 0.3mmol are dissolved in the 2.4mmol oleic acid, to form clarifying homogeneous solution.This solution is cooled to after 60 ℃, adds Se solution (the TOP-Se solution of 1M), 5g cetylamine (HDA) and 2g trioctylphosphine oxide (TOPO) (TOPO) and the 20mL hexane of 2.4mL; Then this solution is transferred in the Parr reactor 4950 of 100mL and used N
2Gas purges.Under agitation this mixture is heated to 320 ℃ and under this temperature, kept 30 minutes-3 hours rapidly.Then, by removing heating and cooling reaction is stopped.By easy centrifugal/dispersion steps come that purifying obtains nanocrystalline, promptly can collecting precipitation nanocrystalline also carries out drying or sedimentary product (for example: be used for hexane) storing is dissolved in organic solvent again.
2.3 synthesis of ternary quantum dot MgFe
2O
4
Under 320 ℃, 0.4mmol magnesiumcarbonate and 0.4mmol Iron diacetate are dissolved in the 3.0mmol oleic acid, to form clarifying homogeneous solution.This solution is cooled to after 60 ℃, adds 5g oleyl amine and 20mL hexane; Then this solution is transferred in the Parr reactor 4950 of 100mL and and purged with N2 gas.Under agitation, mixture is heated to 320 ℃ and under this temperature, kept 30 minutes-3 hours rapidly.Then, by removing heating and cooling reaction is stopped.After centrifugal, collect also drying precipitated product or sedimentary product (for example: be used for hexane) storing is dissolved in organic solvent again.
2.4 synthetic NiFe
2O
4Nanocrystalline
Under 150 ℃, 1.0mmol nickel acetate and 2.0mmol ferric acetyl acetonade (III) (ironacetylacetonate) are dissolved in the 9.0mmol oleic acid, to form uniform solution.This solution is cooled to after 60 ℃, adds 5mL trioctylamine and 20mL hexane; Then this solution is transferred in the Parr reactor 4950 of 100mL and used N
2Gas purges.Under agitation, mixture is heated to 320 ℃ and under this temperature, kept 30 minutes-1 hour rapidly.Then, by removing heating and cooling reaction is stopped.Wherein, under 150 ℃, 1.0mmol nickel acetate and 2.0mmol acetylacetonate iron (III) are dissolved among the ODE of 9.0mmol oleic acid and 5mL trioctylamine and 5mL, to form uniform solution.Then, under 1atm, follow stirring that this mixture is heated to 320 ℃ and kept 30 minutes-1 hour rapidly under this temperature.By removing heating and cooling reaction is stopped.With the mixture that obtains centrifugal and collect and dry obtain nanocrystalline or will obtain nanocrystallinely (for example: be used for storage hexane) be dissolved in organic solvent again.
3.1 preparation be coated with (CdSe)-ZnS of TOPO nanocrystalline (quantum dot, QD)
It is nanocrystalline to prepare the CdSe that is coated with tri octyl phosphine (TOP)/trioctylphosphine oxide (TOPO) (TOPO) as follows.TOPO (30g) is placed flask, and (～1 holder) was 180 ℃ of dryings 1 hour under the vacuum.Then nitrogen is charged into described flask and this flask is heated to 350 ℃.Preparation following injection liquid: CdMe in inert-atmosphere glove box
2(200mL), 1M TOPSe solution (4.0mL) and TOP (16mL).With above-mentioned injection liquid thorough mixing, the syringe of packing into, and from glove box, shift out.
Remove reaction heating, and adopt single continuous injection that reaction mixture is transferred among the TOPO that brute force stirring.Reheat reaction flask, and temperature is increased to 260-280 ℃ gradually.Reaction is cooled to reaction flask～60 ℃ after finishing, and adding 20mL butanols solidifies to prevent TOPO.Add excessive greatly methyl alcohol and cause particle flocculation.By the centrifugal throw out of from supernatant liquid, isolating; The powder that obtains can be scattered in the multiple organic solvent, thereby preparation seems clear soln.
Under vacuum, the flask that will contain 5g TOPO is heated to 190 ℃ and keep several hrs, is cooled to 60 ℃ then, adds 0.5mL tri octyl phosphine (TOP) afterwards.By syringe the CdSe point that is scattered in the hexane of about 0.1-0.4 μ mol is transferred in the reaction vessel, and extracted out solvent.Zinc ethyl (ZnEt
2) and hexamethyl two silthianes ((TMS)
2S) be used separately as the presoma of Zn and S.In inert-atmosphere glove box, the presoma of equimolar amount is dissolved among the 2-4mL TOP.Pack into above-mentioned precursor solution in the syringe and transfer in the feed hopper that is connected on the reaction flask.After reinforced the finishing, mixture is cooled to 90 ℃ and stirred for several hour.Adding butanols in mixture solidifies when being cooled to room temperature to prevent TOPO.
3.2 prepare water-solubility nanocrystalline by forming master-objective complex compound with γ-Huan Hujing
The hydrophobicity top layer that having of obtaining in 3.1 adopted TOP/TOPO nanocrystalline is dissolved in the mixture of 200 μ L chloroform/hexanes (1: 1).Will about 0.5g γ-Huan Hujing and nanocrystal solution join in the 20mL deionized water.Mixture is refluxed about 8 hours up to forming muddy liquid.Remove most water with Rotary Evaporators, then master-objective the inclusion complex that goes out to form by centrifugation.The solid that the further washing of water is collected is to remove the free cyclodextrin molecular.The host and guest's complex compound that has formed by TOP/TOPO and cyclodextrin that so obtains with solid-state storage nanocrystalline.By supersound process with described nanocrystalline being dissolved in the water, and can be at an easy rate with described nanocrystalline transferring in the water.Have been found that by what master/objective complex compound was protected and nanocrystallinely can stablize considerable time with solid-state form.
The quantum dot that the water-soluble γ-CD that forms by formation host and guest complex compound modifies can be followed the tracks of with optical means.In the time of in γ-Huan Hujing being added to the chloroformic solution that contains the CdSe/ZnS core-shell nano crystalline substance that TOP/TOPO covers, formation nanocrystalline from organic chloroform phase transition to the aqueous solution.Also can use
1The formation of the quantum dot that γ-CD modifies is confirmed in H-NMR, FT-IR wave spectrum and XRD test (not display data).Transmission electron microscope (TEM) and fluoroscopic image show that the quantum dot that forms host and guest's complex compound with γ-Huan Hujing forms high monodispersed particle.Show that CdSe/ZnS core-shell nano crystalline substance (measuring in the water) after forming host and guest's complex compound has core-shell nano crystalline substance that the TOP/TOPO-than unmodified covers (at CHCl
3The middle measurement) higher fluorescence intensity, but maximum emission wavelength does not change.The photoluminescence test shows, the CdSe/ZnS core-shell nano crystalline substance that has formed host and guest's complex compound with γ-Huan Hujing is 7.4 (promptly at pH, under the physiological condition) the PBS damping fluid in highly stable, even demonstrate gratifying stability in the aqueous solution of be respectively 5.0 at pH (being oriented to trilateral upwards) and 3.0 (being oriented to downward trilateral).At last, form the thermostability that the CdSe/ZnS core-shell nano crystalline substance behind host and guest's complex compound demonstrates with γ-Huan Hujing in being heated to 50 ℃ the aqueous solution.
4.1 the preparation coupling has the water-solubility nanocrystalline of polymkeric substance in the aqueous solution
Be coated with the quantum dot of TOPO by the method preparation of describing in 3.1.Then, the quantum dot that is coated with TOPO is dissolved in the chloroform with a large amount of mercaptoethylamines (aminoethylthiol).With ultrasonic 2 hours of mixture, at room temperature place then up to precipitation and form fully.The solid that obtains is collected for several times and by centrifugal with the chloroform washing.To be coated with amino quantum dot then, to be dissolved in the pH value be in 8 the buffered soln, then be added drop-wise to poly-(vinylformic acid) polymkeric substance (based on the molecular-weight average of GPC: in the solution 2000), cover coupling group reagent on as coupling agent with activation with EDC and sulfo--NHS, and at room temperature stirred 30 minutes.
Reaction mixture at first stirred 4 hours at 0 ℃, and at room temperature reaction is spent the night then.The solution dialysed overnight that obtains is also stored after with the nitrogen degassing.By at first with ether with the reaction soln washed twice, and the nanocrystalline solution that is coated with polymkeric substance of centrifugal above-mentioned acidity (pH is adjusted to about 4-5) and carry out further purifying.That will collect by regulating pH value (to 7-8) then nanocrystallinely is dissolved in the water again.
The physical-chemical property that polymer shell of the present invention is nanocrystalline carries out following contrast with the physical-chemical property that only is coated with thiohydracrylic acid (MCA) or aminoothyl mercaptan (aminoethanethol) (CdSe)-ZnS core-shell nano crystalline substance (AET): add H in the nanocrystalline aqueous solution
2O
2, and make H
2O
2Ultimate density reach 0.15mol/l, follow the tracks of chemical conduct with photon spectrum (photospectroscopially).For only with MCA or AET coat nanocrystalline, detected nanocrystalline oxidation immediately and nanocrystallinely in 30 minutes, be precipitated out.On the contrary, be with the nanocrystalline obviously more stable of shell, chemical oxidation just takes place lentamente in the face of chemical oxidation.
4.2 preparation has the water-solubility nanocrystalline of link coupled polymkeric substance in organic solution
Be coated with the nanocrystalline of TOPO and will cover according to embodiment 4.1 preparation and nanocrystallinely be dissolved in the chloroform with excessive 3-thiohydracrylic acid.Said mixture at first carries out about 1 hour sonication, at room temperature places then and spends the night up to form a large amount of throw outs in this solution.By centrifugal collecting precipitate, free 3-thiohydracrylic acid is removed by carry out the several washing with acetone.The quantum dot that is coated with the 3-thiohydracrylic acid that obtains is used the argon gas drying simply, is dissolved in the dry DMF then.In this solution, add excessive EDC and NHS, then at room temperature stir about 30 minutes with activation and form crosslinked interface.Follow powerful the stirring, drip the polyaziridine (Sigma-Aldrich Pte Ltd) that the molecular weight that is dissolved in the dry DMF is 1200 (molecular weight (MW) is suitable for 400-60000 usually) by feed hopper.After polyaziridine solution all adds, at room temperature continue reaction and spend the night, be used for the polymkeric substance second layer is coupled to covering reagent.Under reduced pressure remove the DMF solvent then, then be dissolved in the water by rotary evaporation.By be further purified the quantum dot that is coated with polymkeric substance with the ether washed twice.
5.1 preparation has the water-solubility nanocrystalline of crosslinked shell in the aqueous solution
Be coated with the quantum dot of TOPO with the method preparation of describing in 2.1.Brilliant and excessive greatly 3-thiohydracrylic acid and several pyridines of (CdSe)-ZnS core-shell nano that form therefrom are dissolved in the chloroform.Said mixture carries out about 2 hours supersound process, and at room temperature stirs and spend the night.The throw out that forms by centrifugal collection, with washing with acetone to remove excessive acid.Residue carries out dry simply with argon gas.Then, with nanocrystalline being dissolved in water or the buffered soln that obtains, the described nanocrystalline carboxylic acid molecules that is coated with, this carboxylic acid molecules have formed covering/around the first layer of nanocrystal.Before the use, will be in nanocrystalline in the aqueous solution and carry out centrifugally once more, filter, outgas and 25 ℃ of preservations with argon gas with the strainer of 0.2 μ m.
In order to form crosslinked interface and ensuing and be contained in coating reagent layer polymerization in the second layer, be coated with the nanocrystalline of carboxylic acid and be dissolved in the water-based buffer system above-mentioned.Doubly will add in the nanocrystal solution with excessive 500-1000 as EDC of linking agent (1-ethyl-3-[3-dimethyl aminopropyl]-carbodiimide) and sulfo-NHS (sulfo--N-hydroxy-succinamide).The solution that obtains at room temperature stirred 30 minutes, thereby activation forms the functional group that relates in the crosslinked interface.Follow stirring, will contain nanocrystalline, the EDC that covered carboxylic acid and the mixture of sulfo-NHS and be added drop-wise in diamino-carboxyl ester (the diamino-carboxyl methyl ester) solution that is in the identical damping fluid.Said mixture at room temperature stirred 2 hours, spent the night 4 ℃ of placements then, thereby formed crosslinked interface and will be contained in coating reagent and the first layer covalent coupling in the second layer.For the water-soluble carboxyl (that is, hydrolysis methyl esters key) that discharges diamino-carboxyl ester (diamino-carboxylester) also forms the water miscible second layer thus, then add NaOH and the ethanol of 0.1N, and at room temperature solution was stirred 6 hours in addition.With solution centrifugal with remove various solids and under 4 ℃ the form with the aqueous solution store as stock solution.
The quantum dot that obtains also can be fetched purifying by organic solvent extracting.After reaction (form crosslinked interface and will be contained in coating reagent and the first layer covalent coupling in the second layer) was finished, solution extracted with ethyl acetate, thereby extracts the quantum dot of the band polymer shell with ester surface from organic solvent.Merge the organic solvent obtain thus and also carry out drying, remove organic solvent by rotatory evaporator then and be dissolved in ethanol and the NaOH of 0.1N in, with hydrolyse ester bond and form water-solubility nanocrystalline.Solution at room temperature continues to stir 4 hours, neutralizes then.The settled solution that obtains is centrifugal, with the solid of removing various traces and after the degassing under room temperature the form with the aqueous solution store.
The nanocrystalline physico-chemical property of the shell with crosslinked water soluble that the present invention is obtained carries out following contrast with the physico-chemical property that only is coated with (CdSe)-ZnS core-shell nano crystalline substance of thiohydracrylic acid (MCA) or aminoothyl mercaptan (AET): add H in the nanocrystalline aqueous solution
2O
2, and make H
2O
2Ultimate density reach 0.15mol/L, follow the tracks of chemical conduct with photon spectrum.For only with MCA or AET coat nanocrystalline, detected immediately nanocrystalline oxidation and nanocrystalline in 30 minutes precipitation.On the contrary, band shell of the present invention nanocrystalline in the face of chemical oxidation obviously more stable, chemical oxidation just takes place lentamente.
In further testing (not display data), as CdSO with 0.1M
4When solution only added in the brilliant or band shell of the present invention of (the CdSe)-ZnS core-shell nano that covers with MCA nanocrystalline, the nanocrystalline very fast of the described MCA of being coated with was precipitated out from solution.On the contrary, of the present invention nanocrystallinely stably exist in solution this means to add cadmium ion to the not obviously effect of nanocrystalline stability.
Similarly, compare with being coated with the nanocrystalline of MCA, the nanocrystalline photochemical stability of described band shell also obviously improves (not display data).When being exposed to the UV light time that wavelength is 254nm, find that the nanocrystalline of the above-mentioned MCA of being coated with was precipitated out in 48 hours, and nanocrystalline 4 Tian Bao that continue of band shell of the present invention keep steady calmly from solution.Find that also fluorescence intensity keeps stable for a long time.
5.2 preparation has the water-solubility nanocrystalline of crosslinked shell in organic solution
Be coated with the nanocrystalline of TOPO and will this nanocrystalline and excessive (3-N-sulfur alcohol)-1 according to embodiment 4.1 preparation, (pentane-(3-N-ethylthiol)-1 5-diamine) is dissolved in the chloroform 5-pentamethylene diamine together, is used to form the first layer.Mixture is at room temperature placed and is spent the night.By the precipitation that centrifugal collection forms, wash with methyl alcohol then, carry out dry simply with argon gas.Nanocrystallinely be dissolved in (50mL) in the dry DMF with what obtain.
In another flask; with 3; 3-diethyl-carboxylicesters-1; 5-pentane dicarboxylic acid (pentane-3; 3-diethyl-carboxylic ester-1; 5-dicarboxylic acid) (is contained in the second layer) with 5 normal EDC and NHS and is dissolved among the DMF, and under nitrogen protection, at room temperature stirred 20 minutes as coating.This solution is added in the nanocrystal solution lentamente, thereby make described nanocrystalline and coating covalent coupling.At room temperature the solution stirring that obtains after 2 hours, is used the rotary evaporation vapourisation under reduced pressure DMF of system solvent.The slurry that obtains is dissolved in the 5mL water, adds the EtONa/EtOH solution of 5mL 1M then, thereby and under the room temperature restir 2 hours in the second layer, form the water miscible key that is exposed to solvent.Wash twice of the solution (5mL * 2) that obtains with ether, thereby remove the additive or the unreacted starting raw material of various traces.HCl aqueous solution neutralization with 0.1N is used for storing then.Be coated with the nanocrystalline of polymkeric substance and nanocrystalline being dissolved in the water again carried out further purifying by centrifugal in acidic solution by the pH value of regulator solution.
6.1 preparation amphipathic polymkeric substance
Be in the exsiccant CHCl of 300mL to 1g
3In poly-(iso-butylene-alt-maleic anhydride) solution in, add amine separately, then add DIPEA (1mL), and this mixture stirred 16 hours at 50 ℃.Boiling off CHCl
3Afterwards, above-mentioned materials is suspended in water, described glassware for drinking water has with respect to the excess NaOH slightly of the carboxyl on the polymer backbone.After boiling off water and DIPEA, residue is dissolved in the water and carries out several days dialysis with respect to water.With the NaOH of 1M solution being basified to pH is 11, and after then evaporating, obtains product.Described poly-(iso-butylene-alt-maleic anhydride) spontaneously and high productivity react with monofunctional compound and dual functional at least compound (second component herein).
The representative data that forms interested serial amphipathic polymkeric substance 1-5 is provided below.According to the scheme of front, by n-octyl amine being grafted to synthetic described amphipathic polymkeric substance on poly-(iso-butylene-alt-maleic anhydride) with different molar ratios.
Polymkeric substance 1
(0.05g, 0.4mmol) reaction obtains crystalline product 1 (0.86g, 59%) to poly-(iso-butylene-alt-maleic anhydride) 6000 with octylame.
1H-NMR(400MHz，D
2O)δ：3.25-2.90(m，9H)、2.59(bs，39H)、2.08(bs，39H)、1.95-1.35(m，81H)、1.34(bs，62H)、1.13-0.65(m，238H)。Target is formed: carboxyl 97%, decoylamide 3%; Detected composition: carboxyl 96%, decoylamide 4%.
Polymkeric substance 2
(0.15g, 1.2mmol) reaction obtains crystalline product 2 (0.97g, 64%) to poly-(iso-butylene-alt-maleic anhydride) 6000 with octylame.
1H-NMR(400MHz，D
2O)δ：3.30-2.90(m，23H)、2.59(bs，38H)、2.42-1.40(m，152H)、1.23(bs，116H)、1.15-0.70(m，238H)。Target is formed: carboxyl 91%, decoylamide 9%; Detected composition: carboxyl 89%, decoylamide 11%.
Polymkeric substance 3
(0.42g, 3.2mmol) reaction obtains crystalline product 3 (1.06g, 63%) to poly-(iso-butylene-alt-maleic anhydride) 6000 with octylame.
1H-NMR(400MHz，D
2O)δ：3.28-2.85(m，47H)、2.60(bs，37H)、2.41-1.60(m，81H)、1.47(bs，68H)、1.24(bs，253H)、1.12-0.75(m，286H)。Target is formed: carboxyl 75%, decoylamide 25%; Detected composition: carboxyl 75%, decoylamide 25%.
Polymkeric substance 4
(0.84g, 6.5mmol) reaction obtains crystalline product 4 (1.63g, 88%) to poly-(iso-butylene-alt-maleic anhydride) 6000 with octylame.
1H-NMR(400MHz，D
2O)δ：3.25-2.85(m，72H)、2.60(bs，34H)、2.40-1.65(m，73H)、1.48(bs，87H)、1.24(bs，379H)、1.12-0.65(m，317H)。Target is formed: carboxyl 50%, decoylamide 50%; Detected composition: carboxyl 61%, decoylamide 39%.
Polymkeric substance 5
6.2 synthesizing nanocrystalline (quantum dot (QD)/polymkeric substance assembly
The QD of 2mg purifying is dissolved among the THF (2mL), adds the polymers soln of 0.5mL 1.4mM, add 5mL water then.With rotatory evaporator mixture is concentrated to 1mL.Turbid water suspension filters with the strainer of 0.8 μ m, and strainer washs with the 5mL pure water.With hydrophilic strainer (0.2 μ m) filtering supernatant once more, obtain the clarifying QD aqueous solution according to same step.Remove excessive water with rotatory evaporator, thus the concentration that obtains expecting.
Above-mentioned polymkeric substance 1-5 is used for the nanocrystalline water of transferring to.Based on the absorption of QD/ polymkeric substance assembly, the quantum dot of estimating 10-80% is by the suspension step.But this productive rate depends on employed polymkeric substance strongly, even more depends on the purity (the excessive formation that causes aggregate of hydrophobic ligand) of QD.Then detected the suspending efficiency of polymkeric substance 1-5.Bring into use the identical QD of original bulk that is among the THF, use the identical polymkeric substance 1-5 of concentration in water, but obtain the different QD (calculating) of concentration in water with the optics absorptiometer.The ultimate density of QD in water depends on given polymkeric substance QD is suspended in ability in the water.It is more favourable that discovery has the polymkeric substance of the n-octyl group that more is connected on the polymer backbone, and this follows a total observed result, based on hydrophobic-hydrophobic interaction, the quantity of binding site (anchoring point) (herein being hydrophobic n-octyl chain) is many more, and the stability that gives assembly is just high more.Polymkeric substance 5 has the molar mass value higher 10 times than polymkeric substance 1-4, and the concentration of QD is lower in the final aqueous solution, and this may be owing to having formed aggregate (almost not having quantum dot to attracted on the same polymer chain) and the problem relevant with filtration step.Purifying with TOPO, TOP and the cetylamine removed in the QD solution modestly is the key that forms stable QD/ polymkeric substance assembly effectively.Residual alkyl part has hindered monodispersed micellar probably and has formed and promoted flocculation.With polymer overmold QD and transfer in the water QD not that the basic luminosity to QD produces any remarkable influence.Although absorption spectrum demonstrates slight variation, the width of emission maximum place wavelength and emmission spectrum remains unchanged substantially.
6.2.1 clad nano crystalline substance
(for example: the CdSe/ZnS quantum dot that TOPO coats) coat described hydrophobic nano crystalline substance (quantum dot (QD)) by the aqueous solution that the hydrophobic nano crystalline suspension is also then added polymkeric substance in THF.Remove THF by evaporation, obtain the colloidal solution of the quantum dot of stable polymer coating.The solution that obtains is clarification, transparent, and demonstrates secular optical stability and colloidal stability.It should be noted, can on any nanoparticles matter, carry out above-mentioned coating process usually, need not to consider the surface of described nano particle.
6.3 embodiment 4:NIPAM quantum dot copolymerization
In the presence of suitable initiator, carry out polymerization by in water, directly Acrylic Acid Monomer and the QD that is coated with polymkeric substance being mixed or a kind of composition being joined in the solution of another kind of composition.(for example: the concentration of temperature, initiator, composition) can obtain different big or small microballoons, described microballoon is embedded with the QD of different quantities, and described QD is covalently bound to polymer chain with reaction conditions to depend on employed polymkeric substance.
Typical polymkeric substance step:
In the 50mL three-necked flask, by 15 vacuum/argon gas find time and with NIPAM (0.0503g), be coated with solution and the 20mL water deoxygenation of the QD (8mg) of acrylic ester polymer-ammonium salts.Temperature is elevated to 70 ℃ and add initiator K
2S
2O
8(0.0319g is in the H of 1mL
2Among the O).Then in 75 minutes, add the H that is in 4mL
2Linking agent MBAAM (0.0285g) among the O and the solution of NIPAM (0.2526g).After interpolation is finished, mixture is kept 4 hours again at 71 ℃, and be cooled to room temperature.By dialysis (film of 50kD) thus and centrifugally remove bigger particle and carry out purifying.Therefore, acquisition has the aqueous solution of the PNIPAM subparticle of QD.
The direct crosslinking polymerization of quantum dot
By in the aqueous solution of the quantum dot that is coated with polymerisable amphiphilic polymer, adding initiator (as K
2S
2O
8) and carry out polymerization.But the crude product mixture dialysis is obtained water treatment and suspensible solid polymer membrane, and this polymeric film load has high-load QD.
Typical polymerization procedure:
In the flask of 50mL, find time and will be coated with the QD (8mg) of acrylamide polymer-sodium-salt form and the water deoxygenation of 20mL by 15 vacuum/argon gas.Temperature is brought up to 70 ℃ and add initiator K
2S
2O
8(0.0319g is in the H of 1mL
2Among the O).Kept temperature of reaction 6 hours.Carry out purifying by dialysis (film of 50kD).Purification obtains having the water-soluble polymers network of high density QD.
6.4QD micro-emulsion polymerization and copolymerization
[00206] the polymeric material that has a QD (for example: described in the embodiment 5.1-5.2) of coating with polymerizable functional group (described in embodiment 5.3) be used for self-polymerization and with other water-soluble monomer in the copolymerization of reverse microemulsion process.Acquisition is at the controlled microballoon of scope interior diameter of 400nm-10 μ m.The fluorescent lifetime of described microballoon prolongs.
Micro emulsion polymeric typical polymerization step:
(Span 80, solution 0.23g) 1 hour by the dehydrating sorbitol monooleate in the paraffin oil (parafin oil) that is in 10mL to make argon gas.(0.15g, 1.32mmol), N, (0.013g, 0.06mmol), the volume of the QD of 8mg and 10mg polymkeric substance (similar with 1.3.2) is that the aqueous solution of 1mL adds in the oil phase, and argon gas continued bubbling 1 hour to N '-methylene bisacrylamide again will to contain NIPAM.Emulsion 40 ℃ ultrasonic 1 minute, at room temperature vibrated 1 hour with laboratory vortex vibrator then.To stablize and uniformly emulsion be poured on the Petri dish (Petri dish), under 5-15 ℃ the temperature with the irradiation 4 hours in the cross-linking apparatus of logical nitrogen of UV lamp, then placement 16 hours under the condition of in inert atmosphere, not shining.By adopting hexane repeatedly to wash with centrifugal and adopt water repeatedly to wash purification with the centrifugal PNIPAM of carrying out latex subsequently.
Claims (44)
1. a kind of plant, this plant contains at least a nanocrystalline.
2. plant according to claim 1, wherein, the described at least a nanocrystalline nanocrystalline group of forming that is selected from by following type:
The adulterated metal oxide of rare earth metal, the chemical formula of the adulterated metal oxide of this rare earth metal is MeAl
2O
4: Re or Me
4Al
14O
25: R;
Bielement nano crystalline substance, the chemical formula of this bielement nano crystalline substance are M1A or M1O;
Ternary nanocrystals, the chemical formula of this ternary nanocrystals are M1M2A, M1AB or M1M2O;
And
Quaternary nanocrystals, the chemical formula of this quaternary nanocrystals are M1M2AB;
Wherein, M1 in described bielement nano crystalline substance, ternary nanocrystals and the quaternary nanocrystals and M2 are a kind of metal in the II family, III-th family, IV family and the group VIII that are selected from periodic system of elements independently; And if exist, then A and B are independently of one another for being selected from the VI family of periodic system of elements or the element of V family; And
Wherein, the Me in the adulterated metal oxide of described rare earth metal is selected from the group of being made up of Ca, Sr and Ba; And
Re in the adulterated metal oxide of described rare earth metal is at least a element that is selected from the group that Tb, Dy, Nd, Eu and Tm form.
3. plant according to claim 1 and 2, wherein, the described at least a nanocrystalline cadmium that do not comprise.
4. according to any described plant among the claim 1-3, wherein, described at least a nanocrystalline be water miscible.
5. plant according to claim 4 wherein, covers reagent and is connected on the described nanocrystalline surface, and wherein said covering reagent and water soluble molecules formation host and guest complex compound.
6. plant according to claim 5, wherein, described covering reagent is the molecule with following molecular formula:
H
aX-Y-Z，
Wherein,
X is the end group that is selected from S, N, P or O=P,
A is the integer of 0-3,
Y is the group with at least three backbone atoms, and
Z is hydrophobic end group.
7. plant according to claim 5, wherein, described water soluble molecules is to contain the compound that is exposed to the polarity of solvent group.
8. plant according to claim 7, wherein, described water soluble molecules is selected from the group that carbohydrate, ring polyamines, cyclic peptide, calixarene, crown ether and branch-shape polymer are formed.
9. plant according to claim 4, wherein, described at least a nanocrystalline containing:
Cover reagent, this covering reagent is connected to described nanocrystalline surface and forms the first layer, and this covering reagent has at least two coupling group;
Lower molecular weight coats reagent, and this coatings reagent formation second layer also has at least two coupling parts with described coating reagent covalent coupling; And
At least a water soluble group, this water soluble group are used to give the described second layer with water-soluble.
10. plant according to claim 4, wherein, described at least a nanocrystalline containing:
Cover reagent, this covering reagent is connected to described nanocrystalline surface and forms the first layer, and described covering reagent has at least one coupling group;
Polymkeric substance, this polymer formation second layer also has at least one and the coupling part of at least one coupling group covalent coupling of described covering reagent.
11. according to claim 9 or 10 described plants, wherein, described covering reagent is the molecule with following molecular formula:
Wherein,
X is the end group that is selected from S, N, P or O=P,
Ra is the part that contains at least 2 backbone c atoms,
Y be selected from N, C ,-COO-or-CH
2O-,
Z is the part that contains polar functional group,
K is 0 or 1,
M is the integer of 1-3,
N is the integer of 0-3, and
N ' is the integer of 0-2, and wherein n ' is selected as satisfying the valence state requirement of Y.
12. plant according to claim 10, wherein, the molecular formula of described polymkeric substance is:
Wherein,
J is that at least one coupling group to described covering reagent has reactive coupling part, and
M is at least 1 integer.
13. plant according to claim 9, wherein, the lower molecular weight coating reagent that is contained in the described second layer comprises the water soluble molecules with following general formula:
Wherein,
T is a hydrophilic parts,
Rc is the part that contains at least 2 backbone c atoms,
G is selected from N, P, C or Si,
Z ' is the coupling part,
M ' is 2 or 3,
N is 1 or 2, and
N ' is 0 or 1, and wherein n ' is selected as satisfying the valence state requirement of G.
14. plant according to claim 4, wherein, the amphiphilic polymer by noncovalent interaction or covalent interaction is contained on the surface of described at least a at least one in nanocrystalline, and the general formula of described amphiphilic polymer is as follows:
Wherein, m, o and p be independently of one another for being selected from the integer of about 3-400, and wherein m+o+p be selected from the scope of about 10-10000,
R
2Be first aliphatic group, the main chain of this first aliphatic group has the heteroatoms that about 3-20 carbon atom and 0 to about 3 are selected from the group that N, O, S, Se and Si form, and
R
3Be second aliphatic group, the main chain of this second aliphatic group has about 3-80 carbon atom and 0 to about 40 heteroatomss that are selected from N and O,
R wherein
3But group with copolymerization.
15. according to any described plant among the claim 1-14, wherein, the described nanocrystalline gas first portion that is contained in described plant or all on the outside surface.
16. plant according to claim 15, wherein, the described nanocrystalline gas first portion that is contained in described plant.
17. according to claim 15 or 16 described plants, wherein, the gas first portion of described plant is flower and/or the leaf of plant.
18. according to any described plant in claim 1-15 or 17, wherein, described plant is artificial plant or dried plant, this artificial plant is made by the mixture of at least a polymkeric substance, paper, tinsel or above-mentioned materials.
19. according to any described plant among the claim 1-18, wherein, described plant is a flowering plant.
20. plant according to claim 19, wherein, described plant is selected from the group of being made up of the plant of the Rosaceae, silk ball section, the orchid family, silk ball section, hyacinthaceae, Begoniaceae, Labiatae, composite family, Mang ox seedling section, Solanaceae, Liliaceae, Primulaceae, Oenotheraceae, Violaceae, Gesneriaceae, Malvaceae, Bromelia family, Araeceae, Ericaceae, Theaceae and Nyctaginaceae.
21. plant according to claim 19; wherein, described plant is selected from the plant in the group of being made up of rose, orchid, laurustinus, jacinthe, Flower of Evans Begonia, lavandula angustifolia, Garden Dahlia, Flos Pelargonii, petunia, turmeric, flower of Greenish Lily, Flower of Beltleaf Primrose, violet, Herba Leibnitziae, gloxinia, the rose of Sharon, pineapple, Cyclamen persicum, the red palm, rhododendron, Flower of Lesser Bougainvillea and Flower of Japanese Camellia.
22. plant according to claim 20, wherein, described orchid is selected from the subfamily of the orchid family, and it is selected from by blue subfamily, tree orchid subfamily, Herba vanillae Planifoliae subfamily, lady's slipper subfamily and intends the group that blue subfamily is formed.
23. according to any described plant among the claim 1-22, wherein, this plant also contains organic dye.
24. plant according to claim 23, wherein, described organic dye is a fluorophore.
25. plant according to claim 23, wherein, described organic dye is selected from the group of being made up of printing ink, chromophore, fluorescent yellow and fluorescein, and described chromophore is azo-compound, Lyeopene, β-Hu Luobusu and cyanin for example.
26. with at least a nanocrystalline method of giving plant dyeing, this method comprises:
Provide and contain at least a nanocrystalline solution, described nanocrystalline being dissolved in the described solution;
Described plant is contacted with described solution.
27. method according to claim 26, wherein, this method comprises:
Described plant roots is immersed in the described solution, and perhaps the end of the stem that the stem of described plant is cut and will cut is immersed in the described solution.
28. method according to claim 26,, wherein, this method comprises:
Gas first portion or the whole strain plant of described plant are contacted with described solution.
29. method according to claim 28, wherein, described contact comprises described solution impregnation or is sprayed on the gas first portion or whole strain plant of plant.
30. according to claim 26 or 27 described methods, wherein, described at least a nanocrystalline be the mixture of any defined organic dye among any defined nanocrystalline or nanocrystalline and claim 23-25 among the claim 1-14.
31. according to any described method of claim 26-30, wherein, described solution contains the suitable solvent or the mixture of solvent, in the described at least a nanocrystalline mixture that is dissolved in described solvent or solvent.
32. method according to claim 31, wherein, described solvent is aprotic solvent and/or non-polar solvent or protonic solvent.
33. method according to claim 32, wherein, described non-polar solvent is selected from the group of being made up of the mixture of mineral oil, hexane, heptane, hexanaphthene, benzene, toluene, pyridine, methylene dichloride, chloroform, tetracol phenixin, dithiocarbonic anhydride, dioxane, ether, 1-octadecylene, 9-octadecylene, diisopropyl ether, ethylene glycol monobutyl ether, tetrahydrofuran (THF) and above-mentioned solvent.
34. according to any described method among the claim 26-33, wherein, described at least a nanocrystalline concentration is about 0.001-1mol/L.
35. according to any described method among the claim 26-34, wherein, described solution also contains organic dye.
36. method according to claim 35, wherein, described organic dye is a fluorophore.
37. method according to claim 35, wherein, described organic dye is selected from the group of being made up of printing ink, chromophore, fluorescent yellow and fluorescein, and described chromophore is azo-compound, Lyeopene, β-Hu Luobusu and cyanin for example.
38. method according to claim 31, wherein, described solvent is high boiling solvent.
39. according to the described method of claim 38, wherein, described solvent is selected from the group of being made up of 1-octadecylene and 9-octadecylene.
40. among the claim 1-14 among any defined nanocrystalline or nanocrystalline and claim 23-25 the mixture of any defined organic dye be used for plant is carried out painted purposes.
41. according to the described purposes of claim 40, wherein, the gas first portion of described plant is colored.
42. according to the described purposes of claim 41, wherein, by make plant with containing that the nanocrystalline solution that is dissolved in the suitable solvent contacts with described gas first portion dyeing.
43. according to the described purposes of claim 42, wherein, described contact comprises that the end of the stem that described plant roots is immersed in the described solution or the stem of described plant is cut and will cut immerses in the described solution.
44. according to the described purposes of claim 43, wherein, described contact comprises described solution impregnation or is sprayed on the gas first portion or whole strain plant of described plant.
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|---|---|---|---|
| US12128708P | 2008-12-10 | 2008-12-10 | |
| US61/121,287 | 2008-12-10 |
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| JP (1) | JP2010150254A (en) |
| CN (1) | CN101955774A (en) |
| SG (1) | SG162679A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045240A (en) * | 2011-10-17 | 2013-04-17 | 海洋王照明科技股份有限公司 | Thulium doped strontium aluminate up-conversion luminescent material, preparation method and application thereof |
| CN108338437A (en) * | 2018-02-08 | 2018-07-31 | 陈颖魁 | Ultraviolet photoluminescence is manually spent |
| CN109673303A (en) * | 2019-02-19 | 2019-04-26 | 湖南省园艺研究所 | A kind of florescence control method postponing cuckoo flowering time |
| CN110975805A (en) * | 2019-11-26 | 2020-04-10 | 辽宁石化职业技术学院 | Preparation method and application of biochar for reducing enrichment effect of vegetables on Pb (II) in soil |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL266444A (en) * | 2019-05-05 | 2019-07-31 | Dotz Nano Ltd | Tagged plant material and method for identifying same |
| CN110447497A (en) * | 2019-08-16 | 2019-11-15 | 厦门市园林植物园 | A method of promote noble woman begonia to bloom |
| CN114524470B (en) * | 2022-02-24 | 2023-06-02 | 安徽工程大学 | Nickel ferrite nanoparticle and green synthesis method and application thereof |
-
2009
- 2009-12-08 SG SG200908156-3A patent/SG162679A1/en unknown
- 2009-12-10 CN CN2009110002888A patent/CN101955774A/en active Pending
- 2009-12-10 JP JP2009280695A patent/JP2010150254A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045240A (en) * | 2011-10-17 | 2013-04-17 | 海洋王照明科技股份有限公司 | Thulium doped strontium aluminate up-conversion luminescent material, preparation method and application thereof |
| CN103045240B (en) * | 2011-10-17 | 2014-10-15 | 海洋王照明科技股份有限公司 | Thulium doped strontium aluminate up-conversion luminescent material, preparation method and application thereof |
| CN108338437A (en) * | 2018-02-08 | 2018-07-31 | 陈颖魁 | Ultraviolet photoluminescence is manually spent |
| CN109673303A (en) * | 2019-02-19 | 2019-04-26 | 湖南省园艺研究所 | A kind of florescence control method postponing cuckoo flowering time |
| CN110975805A (en) * | 2019-11-26 | 2020-04-10 | 辽宁石化职业技术学院 | Preparation method and application of biochar for reducing enrichment effect of vegetables on Pb (II) in soil |
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| JP2010150254A (en) | 2010-07-08 |
| SG162679A1 (en) | 2010-07-29 |
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