CN105586041A - Amphoteric quantum dots as well as preparation method and application thereof - Google Patents

Amphoteric quantum dots as well as preparation method and application thereof Download PDF

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CN105586041A
CN105586041A CN201511025173.XA CN201511025173A CN105586041A CN 105586041 A CN105586041 A CN 105586041A CN 201511025173 A CN201511025173 A CN 201511025173A CN 105586041 A CN105586041 A CN 105586041A
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quantum dot
water
soluble
surfactant
sexes
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CN105586041B (en
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赖璐
李中宝
梅平
刘义
颜学敏
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Yangtze University
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C09K11/582—Chalcogenides
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • C09K11/883—Chalcogenides with zinc or cadmium

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Abstract

The invention relates to the field of nano material preparation, in particular to amphoteric quantum dots as well as a preparation method and an application thereof. According to the amphoteric quantum dots, water-soluble quantum dots are taken as matrixes, the surfaces of the water-soluble quantum dots are modified by alkyl sulfhydryl with the carbon atom number ranging from 8 to 18, alkyl sulfhydryl is combined with a quaternary ammonium salt type cationic surfactant and an anionic Gemini surfactant, the water-soluble quantum dots are metallic water-soluble quantum dots, and the sizes of the water-soluble quantum dots range from 1 nm to 15 nm. The sizes of the amphoteric quantum dots can range from 5 nm to 15 nm, and fluorescence emission can be adjusted in the range from 370 nm to 800 nm. The amphoteric quantum dots have excellent fluorescence performance in the pH range of 1-14, have good stability and uniform dispersion in a biological liquid and have wide application prospect in multiple fields, and serum protein has small nonspecific adsorption capacity on the surfaces of the quantum dots.

Description

A kind of both sexes quantum dot and its preparation method and application
Technical field
The present invention relates to field of nano material preparation, particularly, relate to a kind of both sexes quantum dot, andThe preparation method and application of this both sexes quantum dot.
Background technology
Quantum dot (QDs), can be described as again semiconductor nano, normally by II-VI, and III-V, or IV-VIFamily's element composition, particle diameter is generally between 1～10nm. When semi-conductive size be less than or with exciton bohr halfWhen footpath is suitable, can produce obvious quantum confined effect, continuous being with becomes discrete energy levels structure, because ofThis has special optics and electrology characteristic. Compared with traditional organic fluorescent dye, quantum dot has glimmeringLight transmitting is adjustable, emission spectrum is narrow and symmetrical, absorption spectrum is wide and unique optics such as good light stabilityCharacteristic. Therefore, quantum dot is applied to the aspect such as biological study and clinical medicine more and more widely, asThe detection of inside and outside imaging, tumour and treatment, immunohistochemistry detection, medicament transport and treatment, lifeThing sensing and individual particle spike etc.
The particle diameter of quantum dot is little, has huge surface area. In order to make its stable existence, or will haveThe quantum dot that machine is prepared mutually goes to water, need to carry out finishing to quantum dot. At present, quantum dot tableThe method of modifying of face mainly comprises:
One, utilize stronger combination between the metallic atom such as sulphur atom and Cd, Zn in sulfydryl,Adopt the little molecule of sulfydryl to carry out finishing, as mercaptopropionic acid (MPA), N-acetyl-L-cysteine(NAC), glutathione (GSH) and sulfydryl hendecanoic acid (MUA) etc.;
Two, utilize hydrophobic interaction, adopt amphipathic nature polyalcohol carry out finishing, as polyethylene glycol,Phosphatide, shitosan etc.;
Three, utilize covalent coupling or non-specific adsorption effect, adopt large biological molecule to carry out finishing,As oligonucleotide, haemocyanin etc.
Above-mentioned preparation method has their own characteristics each, but also has the following disadvantages:
One, there is following problem in the small numerator modified quantum dot of sulfydryl: the pH scope of application is too narrow; Giving birth toIn logistics body, salinity is too high easily causes quantum dot generation coagulation, thus fluorescent quenching; And serumCan there is comparatively serious non-specific adsorption on quantum dot surface in albumen, thereby produce bio-toxicity.
Although two, the quantum dot good stability of amphipathic nature polyalcohol finishing, the hydration grain of quantum dotFootpath is excessive. The nano particle of small particle diameter more easily enters cell, can effectively realize its function. Polymerization simultaneouslyThe quantum dot surface charge density that thing is modified is excessive, can occur comparatively serious with the albumen in biofluidNon-specific adsorption, thus bio-toxicity produced.
Although the quantum dot fluorescent stability that three, large biological molecule is modified is good, good biocompatibility. But amountThe hydration particle diameter of son point is also larger. The method of the covalent coupling of quantum dot and albumen is also too loaded down with trivial details, operationDifficulty is large. In addition, the cost of large biological molecule method of modifying is higher, is not suitable for preparation in enormous quantities. Due toThe size of large biological molecule is larger than quantum dot, and therefore the removal difficulty of free large biological molecule is larger, quantumThe purifying of point is more complicated.
Summary of the invention
The object of the invention is to overcome the pH scope of application that prior art exists is too narrow, particle diameter is too large and/Or the problem such as fluorescent stability is bad, a kind of both sexes quantum dot is provided, and this both sexes quantum dotPreparation method and application. The particle diameter of both sexes quantum dot of the present invention can be in the scope of 5-15nm, glimmeringLight transmitting can be adjustable in the scope of 370-800nm, and both sexes quantum dot of the present invention existsIn the scope of pH=1～14, all there is good fluorescence property, good stability in biofluid, pointEvenly loose, and haemocyanin is little in the non-specific adsorption amount on quantum dot surface, in multiple fields allHave wide practical use.
The present inventor finds, if the alkyl hydrosulfide that is first 8-18 by carbon number is modified at grainThe surface of the less water-soluble quantum dot in footpath itself, then makes quaternaries cation by hydrophobic effectThe chain alkyl of surfactant molecule and anionic type Gemini surface active agent molecule and alkyl hydrosulfideCombine, just can obtain having the both sexes quantum dot of negative ions, completed thus the present invention.
The invention provides a kind of both sexes quantum dot, this both sexes quantum dot is taking water-soluble quantum dot as baseBody, this water-soluble quantum dot surface is at least modified with the alkyl hydrosulfide that carbon number is 8-18, and this alkaneBase mercaptan is tied mutually with quaternary cationic surfactant and anionic type Gemini surface active agentClose, described water-soluble quantum dot is metallic water-soluble quantum dot, and described water-soluble quantum dotParticle diameter is 1-15nm.
The present invention also provides a kind of method of preparing both sexes quantum dot, and the method comprises the following steps:
1) solution of alkyl hydrosulfide and the metallicity of mercaptopropionic acid modification that carbon number is 8-18 will be containedThe aqueous solution of water-soluble quantum dot carry out the first contact, the particle diameter of described water-soluble quantum dot is1-15nm；
2) will after the product removal solvent after the first contact, be dispersed in organic solvent;
3) by the aqueous solution of quaternary cationic surfactant and anionic type Gemini surface activeOne and step 2 in the aqueous solution of agent) products therefrom carries out second and contacts, then stratification abandoningFall organic layer, gained water is dialysed for the first time and obtained the quantum dot aqueous solution;
4) by the aqueous solution of quaternary cationic surfactant and anionic type Gemini surface activeAnother kind and step 3 in the aqueous solution of agent) products therefrom carries out the 3rd and contacts, then that gained is water-solubleLiquid is dialysed for the second time.
The both sexes quantum dot that the present invention provides again the method according to this invention to prepare.
The present invention provides both sexes quantum dot of the present invention at gene transfection, biomarker, biology in additionApplication on separation, immune detection, drug targeting release and target imaging.
Compared with prior art, the advantage of product of the present invention and method is at least:
(1) the hydration particle diameter of gained quantum dot is less, can be within the scope of 5～15nm, and fluorescenceBe transmitted in 370～800nm adjustable;
(2) the pH scope of application is wider, and in the scope of pH=1～14, the surface of quantum dot is all with electricityLotus, the repulsive interaction between surface charge has stoped the coagulation of quantum dot, therefore at the model of pH=1～14Enclose the interior good fluorescence property that all has;
(3) good stability, be uniformly dispersed, higher salinity also can not cause the coagulation of quantum dot;
(4) method is more simple, workable, with low cost.
Other features and advantages of the present invention are said the detailed description of the invention part subsequently in detailBright.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description,Be used from explanation the present invention with detailed description of the invention one below, but do not form limit of the present inventionSystem. In the accompanying drawings:
Fig. 1 is the electromicroscopic photograph of the both sexes quantum dot I3 for preparing of embodiment 3.
Fig. 2 is both sexes quantum dot I1～I4 fluorescence spectrum figure prepared by embodiment 1-4.
Fig. 3 is CdTe/ZnS quantum dot and the embodiment 3 that pH MPA that preparation example 5 is made modifiesThe impact of the fluorescence intensity of the both sexes quantum dot I3 making.
Fig. 4 is in cell culture medium, the CdTe/ZnS quantum dot that the MPA that preparation example 5 makes modifiesThe fluorescence intensity of the both sexes quantum dot I3 making with embodiment 3 over time.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that this placeThe detailed description of the invention of describing, only for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of both sexes quantum dot, this both sexes quantum dot is taking water-soluble quantum dot as baseBody, this water-soluble quantum dot surface is at least modified with the alkyl hydrosulfide that carbon number is 8-18, and this alkaneBase mercaptan is tied mutually with quaternary cationic surfactant and anionic type Gemini surface active agentClose, described water-soluble quantum dot is metallic water-soluble quantum dot, and described water-soluble quantum dotParticle diameter is 1-15nm.
In the present invention, " alkyl hydrosulfide with quaternary cationic surfactant and anionicGemini surfactant combines " refer to: the chain alkyl of alkyl hydrosulfide respectively with quaternary ammonium salt sun fromThe chain alkyl of sub-surface activating agent and the chain alkyl of anionic type Gemini surface active agent are by dredgingWater mutual effect and combining.
In the present invention, term " particle diameter " refers to and uses Ma Erwen ZetasizerNano nano particle sizeThe average grain diameter that instrument measures. In the present invention, by by quaternary cationic surfactantMolecule and anionic type Gemini surface active agent molecule are directly attached to quantum dot surface, thereby canThe particle diameter of the both sexes quantum dot of gained is controlled in the scope of 1-15nm.
In the present invention, due to described quaternary cationic surfactant and anionic type Gemini surfaceSurfactant is to combine with the alkyl hydrosulfide of water-soluble quantum dot finishing with molecular conformation, thereforeCan't produce obviously impact to the particle diameter of gained both sexes quantum dot, therefore can think described both sexes quantumThe particle diameter of point equals the particle diameter of described water-soluble quantum dot. In the art, described water-soluble quantum dotParticle diameter is commonly nanoscale, and the particle diameter of the described water-soluble quantum dot that the present invention selects can be 1-15nm,Be preferably 1-10nm, more preferably 2-8nm, most preferably is 2-5nm; Correspondingly, both sexes of the present inventionThe particle diameter of quantum dot can be 1-15nm, is preferably 1-10nm, and more preferably 2-8nm, most preferably is2-5nm。
In the present invention, described water-soluble quantum dot is metallic water-soluble quantum dot, its finishingHaving carbon number is the alkyl hydrosulfide of 8-18, the alkyl hydrosulfide that this carbon number is 8-18 and metallicWater-soluble quantum dot combines by covalent bond. And, the chain alkyl of described alkyl hydrosulfide respectively with seasonThe chain alkyl of ammonium salt cationoid surfactant and the long-chain of anionic type Gemini surface active agentAlkyl combines by hydrophobic interaction. The carbon number of described alkyl hydrosulfide is 8-18, is preferably9-16, more preferably 11-13; Carbochain in described alkyl hydrosulfide can have 0-2 bar side chain, does not preferably haveSide chain, the carbochain in described alkyl hydrosulfide is straight chain; Described alkyl hydrosulfide has at least one sulfydryl officialCan roll into a ball, preferably have 1-2 mercapto functional group, preferably, described mercapto functional group is positioned at the end of carbochainEnd. Described alkyl hydrosulfide can be for example lauryl mercaptan, n-hexadecyl mercaptan and n-octadecane base mercaptanIn one or more, most preferably be lauryl mercaptan.
In the present invention, there is no particular limitation for the kind of described metallic water-soluble quantum dot, for exampleCan be selected from ZnSe quantum dot, CdTe quantum dot, CdTe/ZnS quantum dot and Ag2In S quantum dotOne or more.
In the present invention, with respect to a described water-soluble quantum dot, the described carbon atom of its finishingThe number that number is the alkyl hydrosulfides of 8-18 is can 20-60, is preferably 40-60.
In the present invention, the surface of described water-soluble quantum dot can also be modified with mercaptopropionic acid, with describedThe total number of all molecules that contain sulfydryl of the finishing of water-soluble quantum dot is benchmark, this sulfydryl thirdThe content of acid can be, below 10%, to be preferably below 5%, more preferably below 2%.
In the present invention, described water-soluble quantum dot and described quaternary cationic surfactant andThere is no particular limitation for the proportioning of anionic type Gemini surface active agent, for example, with respect to described in oneWater-soluble quantum dot, the described anionic type Gemini surface active agent that combines with described alkyl hydrosulfideNumber can be 5-15, is preferably 10-15; Combine with described alkyl hydrosulfide described quaternary ammonium salt sun fromThe number of sub-surface activating agent can meet, make described quaternary cationic surfactant with described inThe charge ratio of anionic type Gemini surface active agent is 1.01-1.15:1, specifically can be according to quaternary ammonium saltThe kind of cationoid surfactant is selected charge ratio.
In the present invention, there is no particular limitation for described quaternary cationic surfactant, preferablyBe selected from one in bi-quaternary ammonium salt cationoid surfactant and mono-quaternaries cationoid surfactantKind or multiple. Preferably, described bi-quaternary ammonium salt cationoid surfactant has knot shown in formula (1)Structure, described mono-quaternaries cationoid surfactant has structure shown in formula (2),
In formula (1), m and n are selected from the arbitrary integer in 7-17 independently of one another, and X is halogen;Preferably, m and n are selected from the arbitrary integer in 8-15 independently of one another, and X is fluorine, chlorine, bromine or iodineElement; Further preferably, m and n are selected from the arbitrary integer in 10-12 independently of one another, and X isFluorine, chlorine or bromine element; Particularly preferably, m and n are that 11, X is chlorine or bromine element. Described pair of quaternary ammoniumSalt cationic surfactant for example can be exemplified as N, N '-bis-dodecyl bi-quaternary ammonium salts.
In formula (2), p is selected from the arbitrary integer in 7-17, and X is halogen; Preferably, p choosingArbitrary integer in 8-15, X is fluorine, chlorine, bromine or iodine element; Further preferably, p is selected fromArbitrary integer in 10-12, X is fluorine, chlorine or bromine element; Particularly preferably, p is that 11, X is chlorineOr bromo element. Described mono-quaternaries cationoid surfactant for example can be exemplified as dodecyl threeMethyl ammonium bromide (DTAB), DTAC (DTAC) and cetyl trimethylAmmonium bromide (CTAB).
In the present invention, described anionic type Gemini surface active agent and quaternaries cation surfaceThere is no particular limitation for the amount ratio of activating agent, can calculate according to charge ratio. For example,, when described seasonWhen ammonium salt cationoid surfactant is bi-quaternary ammonium salt cationoid surfactant, described anionThe charge ratio of type Gemini surfactant and quaternary cationic surfactant is 1.03-1.08:1, be preferably 1.04-1.06:1; When described quaternary cationic surfactant is mono-quaternaries classWhen cationic surfactant, described anionic type Gemini surface active agent and quaternaries cationThe charge ratio of surfactant is 1.06-1.15:1, is preferably 1.08-1.12:1.
In the present invention, preferably, described anionic type Gemini surface active agent is for having formula (3)Shown in the Sulfonic Gemini Surfactants of structure,
Wherein, a and b are selected from the arbitrary integer in 7-17 independently of one another, and Y is alkali metal; ExcellentSelection of land, a and b are selected from the arbitrary integer in 8-15 independently of one another, and Y is lithium, sodium or potassium element; EnterPreferably, a and b are selected from the arbitrary integer in 10-12 to step independently of one another, and Y is sodium or potassium element;Particularly preferably, a and b are that 11, Y is sodium or potassium element.
The present invention also provides a kind of method of preparing both sexes quantum dot, and the method comprises the following steps:
1) solution of alkyl hydrosulfide and the metallicity of mercaptopropionic acid modification that carbon number is 8-18 will be containedThe aqueous solution of water-soluble quantum dot carry out the first contact, the particle diameter of described water-soluble quantum dot is1-15nm；
2) will after the product removal solvent after the first contact, be dispersed in organic solvent;
3) by the aqueous solution of quaternary cationic surfactant and anionic type Gemini surface activeOne and step 2 in the aqueous solution of agent) products therefrom carries out second and contacts, then stratification abandoningFall organic layer, gained water is dialysed for the first time and obtained the quantum dot aqueous solution;
4) by the aqueous solution of quaternary cationic surfactant and anionic type Gemini surface activeAnother kind and step 3 in the aqueous solution of agent) products therefrom carries out the 3rd and contacts, then that gained is water-solubleLiquid is dialysed for the second time.
In step 1) in, described in to contain carbon number be that the solution of alkyl hydrosulfide of 8-18 is for by alkyl sulfideAlcohol is dissolved in the solution obtaining in the first organic solvent, wherein alkyl hydrosulfide and described first organic moltenThe volume ratio of agent can be 1:600-1000, is preferably 1:800-900. Described the first organic solventThere is no particular limitation for kind, can be for arbitrarily can be miscible and volatile with alkyl sulfide alcohol and waterOrganic solvent, for example can be selected from one or more in acetone, methyl alcohol and ethanol, be preferably thirdKetone.
In step 1) in, the concentration of the water-soluble quantum dot in the aqueous solution of described water-soluble quantum dot does not haveHaving special restriction, for example, can be 50～500 μ mol/L, is preferably 50-250 μ mol/L, more preferablyFor 80-200 μ mol/L.
In step 1) in, the process of described the first contact comprises: under the condition stirring, by water-solubleThe aqueous solution of quantum dot is added drop-wise in the solution that contains alkyl hydrosulfide, and continues to stir. Described droppingMode has no particular limits, and is preferably quick dropping, and the aqueous solution of described water-soluble quantum dot is existedIn 0.5-2.5min (being preferably 1-2min), dropwise. The condition of described the first contact comprises: temperatureCan be 15-50 DEG C, be preferably 20-30 DEG C, the time can be 20-30h. Described stirring is preferably soonSpeed stirs, and the speed of stirring is for example 200-300r/min.
In step 1) in, the carbon number of described alkyl hydrosulfide is 8-18, is preferably 9-16, more preferablyFor 11-13; Carbochain in described alkyl hydrosulfide can have 0-2 bar side chain, preferably there is no side chain, i.e. instituteThe carbochain of stating in alkyl hydrosulfide is straight chain; Described alkyl hydrosulfide has at least one mercapto functional group, preferablyHave 1-2 mercapto functional group, preferably, described mercapto functional group is positioned at the end of carbochain. Described alkaneBase mercaptan can be for example a kind of in lauryl mercaptan, n-hexadecyl mercaptan and n-octadecane base mercaptan orMultiple, most preferably be lauryl mercaptan.
In step 2) in, the described not special limit of method of product after the first contact being removed to solventDetermine, for example, can adopt the method for decompression distillation. The solvent of removing refers to above-mentioned first organic moltenAgent (containing the solvent in the solution of alkyl hydrosulfide) and water (are in the aqueous solution of water-soluble quantum dotSolvent). When reaching 95%, removal of solvents rate thinks that the process of removing solvent can finish when above.
In step 2) in, will after the product removal solvent after the first contact, be dispersed in organic solvent, forWith step 1) in prepare alkyl hydrosulfide solution described the first organic solvent distinguish mutually, step 2) instituteWith this organic solvent hereinafter referred to as " the second organic solvent ". The kind of described the second organic solvent does not haveHaving special restriction, for example, can be one or more of arene and chloroform, be preferably toluene,One or more in benzene and chloroform.
In step 2) in, described by volume and organic solvent after the product removal solvent after the first contactVolume ratio there is no particular limitation, can be for example 1:800-2000, be preferably 1:1000-1600。
In step 2) in, there is no particular limitation for the mode of described dispersion, for example, can be ultrasonic pointLoose.
In step 3) and step 4) in, by quaternary cationic surfactant and anionicGemini surfactant substep is modified at the quantum dot surface making, the not special limit of sequencingFixed, preferably, in step 3) in select anionic type Gemini surface active agent, in step 4) inSelect quaternary cationic surfactant.
In the present invention, described water-soluble quantum dot and described anionic type Gemini surface active agentMol ratio can be 1:1-3, is preferably 1:1.7-2.4; Described anionic type Gemini surface active agentCan determine according to electric charge with the consumption of quaternary cationic surfactant, for example charge ratio canThink 1:1.01-1.15, specifically can select electricity according to the kind of quaternary cationic surfactantLotus ratio.
In the present invention, the aqueous solution of described quaternary cationic surfactant and described anionAll there is no particular limitation for the concentration of the aqueous solution of type Gemini surfactant, for example, and described quaternary ammoniumThe concentration of the aqueous solution of salt cationic surfactant can be 80-1200 μ molL-1, be preferably250-750μmol·L-1; The concentration of the aqueous solution of described anionic type Gemini surface active agent can be80-1200μmol·L-1, be preferably 250-750 μ molL-1。
In step 3) in, the process of described the second contact comprises: under the condition stirring, by step 2)Product after gained disperses and the aqueous solution and the anionic of quaternary cationic surfactantOne in the aqueous solution of Gemini surfactant is mixed. The condition bag of described the second contactDraw together: temperature can be 30-60 DEG C, is preferably 40-50 DEG C, and the time can be 20-30h. Described stirringBe preferably rapid stirring, the speed of stirring is for example 200-300r/min.
In step 3) in, there is no particular limitation for the method for described dialysis for the first time, normal according to this areaThe dialysis procedure of rule. It is preferably, described that to dialyse for the first time in concentration be 0.5 × 10-2～1.5×10-2In the PBS of mol/L, carry out. Further preferably, saturating for the first time described in carrying outBefore analysing, the product after described the second contact is filtered, for example can be with the filtering head of 0.22 μ mFilter.
In step 4) in, the process of described the 3rd contact comprises: under the condition stirring, by step 3)Product after gained disperses and the aqueous solution and the anionic of quaternary cationic surfactantAnother kind in the aqueous solution of Gemini surfactant mixes. The condition bag of described the 3rd contactDraw together: temperature can be 30-60 DEG C, is preferably 40-50 DEG C, and the time can be 20-30h. Described stirringBe preferably rapid stirring, the speed of stirring is for example 200-300r/min.
In step 4) in, there is no particular limitation for the method for described dialysis for the second time, normal according to this areaThe dialysis procedure of rule. It is preferably, described that to dialyse for the second time in concentration be 0.5 × 10-2～1.5×10-2In the PBS of mol/L, carry out. Further preferably, saturating for the second time described in carrying outBefore analysing, the product after described the second contact is filtered, for example can be with the filtering head of 0.22 μ mFilter.
In the present invention, described water-soluble quantum dot is the metallic water-soluble amount that mercaptopropionic acid is modifiedSub-, the present invention is by step 1) in first contact process described water-soluble quantum dot surface is repaiiedThe alkyl hydrosulfide that most mercaptopropionic acids of decorations are 8-18 by carbon number replaces (preferably whole sulfydrylsThe alkyl hydrosulfide that propionic acid is 8-18 by carbon number replaces). Water-soluble quantum dot described in method of the present inventionKind there is no particular limitation, ZnSe quantum dot, the sulfydryl for example can selected from mercapto propionic acid modifiedThe CdTe quantum dot that propionic acid is modified, CdTe/ZnS quantum dot and the mercaptopropionic acid that mercaptopropionic acid is modified are modifiedAg2One or more in S quantum dot. In the present invention, described water-soluble quantum dot can be boughtObtain also can preparing, the method for preparation can be the routine operation of this area, for example, under passing throughThe method of stating obtains.
1) mercaptopropionic acid (MPA) is modified ZnSe quantum dot
The preparation of Zn precursor: preparation ZnCl2With the mixed aqueous solution of MPA, wherein ZnCl2ConcentrationFor 0.008-0.012mol/L, ZnCl2With the mol ratio of MPA be 1:1.5-2.0. Regulate pH extremely11.2-11.7. Then eliminate the oxygen in environment.
The preparation of NaHSe: under ice-water bath, by Se powder and NaBH4In water, be stirred to water white transparency,Se powder and NaBH4Weight ratio be 1:1.5-1.65, with respect to 1gNaBH4, the consumption of water is18-22mL。
At room temperature, under strong stirring, use in above-mentioned Zn precursor and add above-mentioned NaHSe solution to obtainZnSe precursor solution, wherein [Zn]: [MPA]: [Se]=1:1.1-1.3:1.3-0.5. By described ZnSePrecursor solution is 155-165 DEG C of reaction 10-20 minute in oil bath, can obtain the ZnSe that MPA modifiesQuantum dot. By washed with isopropyl alcohol three times, then by gained solid drying.
2) MPA modifies CdTe quantum dot
The preparation of Cd precursor: preparation CdCl2With the mixed aqueous solution of MPA, wherein ZnCl2ConcentrationFor 0.003-0.005mol/L, ZnCl2With the mol ratio of MPA be 1:1.5-2.0. Regulate pH to 7.5-8.5.Then eliminate the oxygen in environment.
The preparation of Te precursor: under ice-water bath, by Te powder and NaBH4In water, be stirred to water white transparency,Se powder and NaBH4Mol ratio be 1:2.2-2.7, with respect to 1mmolNaBH4, the consumption of water is3.5-4.5mL。
At room temperature, under strong stirring, use in above-mentioned Cd precursor and add above-mentioned NaHTe solution to obtainCdTe precursor solution, wherein [Cd]: [MPA]: [Te]=1:1.5-2.0:0.18-0.22. By described ZnSePrecursor solution is condensing reflux 1.5-2.5 hour in oil bath, can obtain the CdTe quantum that MPA modifiesPoint.
3) MPA modifies CdTe/ZnS quantum dot.
Make according to the method described above the CdTe quantum dot that MPA modifies, by ZnCl2、Na2S、MPABe mixed to get precursor solution with CdTe quantum dot, wherein ZnCl2、Na2The CdTe that S, MPA modifyThe mol ratio of the consumption of quantum dot is 1:0.18-0.22:4.8-5.2, with respect to 1mmolZnCl2, waterConsumption is 35-45mL. Regulating pH value is 10.8-11.2, removes the oxygen in environment, will react mixingThing reacts and within 2.5-4 hour, obtains the CdTe/ZnS core/shell structure quantum dot that MPA modifies at 60-70 DEG C.
4) MPA modifies Ag2S quantum dot.
In inert gas environment, at 105-115 DEG C of temperature, in the ethylene glycol solution of MPA, addAgNO3, wherein the volume ratio of the consumption of MPA and ethylene glycol is 1:90-110, with respect to 100μLMPA，AgNO3Consumption be 0.04-0.06mmol. Be warming up to 145-155 DEG C of reaction 12-20 minute.The centrifugal Ag that obtains MPA modification after washing2S quantum dot solid.
In the present invention, the quantity of the mercaptopropionic acid of described water-soluble quantum dot finishing is not specialLimit, for example, with respect to a described water-soluble quantum dot, the number of the mercaptopropionic acid of finishing isCan 20-60, be preferably 40-60, more preferably 50-60.
In the present invention, the particle diameter of described water-soluble quantum dot can be 1-15nm, is preferably 1-10nm,More preferably 2-8nm, most preferably is 2-5nm; Thereby, the particle diameter of the quantum dot of the present invention obtainingCan be 1-15nm, be preferably 1-10nm, more preferably 2-8nm, most preferably be 2-5nm.
In the present invention, there is no particular limitation for described quaternary cationic surfactant, preferablyBe selected from one in bi-quaternary ammonium salt cationoid surfactant and mono-quaternaries cationoid surfactantKind or multiple. Preferably, described bi-quaternary ammonium salt cationoid surfactant has knot shown in formula (1)Structure, described mono-quaternaries cationoid surfactant has structure shown in formula (2),
In formula (1), m and n are selected from the arbitrary integer in 7-17 independently of one another, and X is halogen;Preferably, m and n are selected from the arbitrary integer in 8-15 independently of one another, and X is fluorine, chlorine, bromine or iodineElement; Further preferably, m and n are selected from the arbitrary integer in 10-12 independently of one another, and X isFluorine, chlorine or bromine element; Particularly preferably, m and n are that 11, X is chlorine or bromine element. Described pair of quaternary ammoniumSalt cationic surfactant for example can be exemplified as N, the two dodecyl bi-quaternary ammonium salts of N '.
In formula (2), p is selected from the arbitrary integer in 7-17, and X is halogen; Preferably, p choosingArbitrary integer in 8-15, X is fluorine, chlorine, bromine or iodine element; Further preferably, p is selected fromArbitrary integer in 10-12, X is fluorine, chlorine or bromine element; Particularly preferably, p is that 11, X is chlorineOr bromo element. Described mono-quaternaries cationoid surfactant for example can be exemplified as dodecyl threeMethyl ammonium bromide (DTAB), DTAC (DTAC) and cetyl trimethylAmmonium bromide (CTAB).
In the present invention, described mono-quaternaries cationoid surfactant can obtain by purchase.Described bi-quaternary ammonium salt cationoid surfactant can obtain by purchase, also can be by being prepared intoArrive, the described method of preparing bi-quaternary ammonium salt cationoid surfactant can comprise the following steps:
Ba) alkylamine of structure shown in formula (4) and dihalo-ethane are refluxed instead in the 3rd organic solventShould, then remove solvent;
Bb) with the 4th organic solvent to step Ba) products therefrom is recrystallized, and to obtain pressed powder rightRear dry;
Wherein e is selected from the arbitrary integer in 7-17, is preferably selected fromArbitrary integer in 8-15, is more preferably selected from the arbitrary integer in 10-12, is particularly preferably 11.
At step Ba) in, the volume ratio of described alkylamine, dihalo-ethane and the 3rd organic solvent is passableFor 5-9:1:30-40. The time of described back flow reaction can be 40-60 hour. Described the 3rd organic moltenAgent is for example isopropyl alcohol. The method of described removal solvent can be decompression distillation.
At step Bb) in, described the 4th organic solvent is for example acetone. Described dry temperature is passableFor 30-60 DEG C, the described dry time can be 16-30 hour, is preferably vacuum drying.
In the present invention, described anionic type Gemini surface active agent and quaternaries cation surfaceThere is no particular limitation for the amount ratio of activating agent, can calculate according to charge ratio. For example,, when described seasonWhen ammonium salt cationoid surfactant is bi-quaternary ammonium salt cationoid surfactant, described anionThe charge ratio of type Gemini surfactant and quaternary cationic surfactant is 1.03-1.08:1, be preferably 1.04-1.06:1; When described quaternary cationic surfactant is mono-quaternaries classWhen cationic surfactant, described anionic type Gemini surface active agent and quaternaries cationThe charge ratio of surfactant is 1.06-1.15:1, is preferably 1.08-1.12:1.
In the present invention, preferably, described anionic type Gemini surface active agent is for having formula (3)Shown in the Sulfonic Gemini Surfactants of structure,
Wherein, a and b are selected from the arbitrary integer in 7-17 independently of one another, and Y is alkali metal; ExcellentSelection of land, a and b are selected from the arbitrary integer in 8-15 independently of one another, and Y is lithium, sodium or potassium element; EnterPreferably, a and b are selected from the arbitrary integer in 10-12 to step independently of one another, and Y is sodium or potassium element;Particularly preferably, a and b are that 11, Y is sodium or potassium element.
In the present invention, described Sulfonic Gemini Surfactants can obtain by purchase, alsoCan be by preparing, the described method of preparing Sulfonic Gemini Surfactants can be passed throughBy N, the two alkyl ethylenediamines of N-and 1,3-the third sultone are that raw material prepares, described N, the two alkyl second of N-The alkyl being connected with N in diamines is the straight chained alkyl of C8-C18, and concrete grammar can comprise following stepRapid:
Sa), by 1,3-the third sultone and above-mentioned N, the two alkyl ethylenediamines of N-are dissolved in the 5th organic solvent, andUnder the protection of inert gas, add hot reflux 20-40 hour, filter and obtain solid;
Sb) by step Sa) gained solid is recrystallized with mixed solvent the 6th organic solvent, thenVacuum drying.
At step Sa) in, with respect to the described N of 1g, the two alkyl ethylenediamines of N-, described 1, in 3-the third sulphurThe consumption of ester is 1.5-2.5g, and the volume of described the 5th organic solvent is 10-20mL. Described the 5th organicSolvent is for example methyl alcohol. Described filtration is preferably decompress filter.
At step Sb) in, described the 6th organic solvent is for example the mixed solvent of methyl alcohol and chloroform, itsVolume ratio can be 1:0.5-2, is preferably 1:1-1.5. Described dry temperature can be30-60 DEG C, the described dry time can be 16-30 hour, is preferably vacuum drying.
Described N, the two alkyl ethylenediamines of N-can be bought also and can prepare. A kind of tool according to the present inventionThe embodiment of body, the preparation method of the Sulfonic Gemini Surfactants of structure shown in formula (3)For: get ethylenediamine in there-necked flask, add absolute ethyl alcohol, under magnetic agitation, drip brominated alkanes (endThe linear paraffin of the C8-C18 that replaced by bromine of some carbon), back flow reaction 40-60h at 70-90 DEG C; Decompression is steamedDesolventize, obtain faint yellow solid powder; By ether washing gained solid several times, until be white in color; WithMixed solvent methyl alcohol-chloroform (volume ratio 1:1.8-2.2) is recrystallized gained pressed powder 2-3 time,White needles pressed powder, vacuum drying 20-40h, gained white needles pressed powder is N, N′-bis-alkaneBase ethylenediamine. Get N, N '-bis-alkyl ethylenediamines and 1,3-the third sultone are dissolved in methyl alcohol, in nitrogen protectionLower heating reflux reaction 20-30h, obtains white solid by the solution decompression suction filtration of gained; With methyl alcohol-chloroformWhite solid is recrystallized, obtains white solid powder, vacuum drying 20-40h, gained white is solidBody powder is the Sulfonic Gemini Surfactants of structure shown in formula (3).
In the present invention, various organic solvents used are roughly the same in occupation mode, require roughly the sameSituation under, these organic solvents can be identical, also can be different.
The both sexes quantum dot that the present invention provides again the method according to this invention to prepare. Of the present invention twoProperty quantum dot particle diameter can be in the scope of 5-15nm, and by regulate quantum dot particle diameter orChoose different quantum dots, can make fluorescent emission wavelength adjustable in 370-800nm, particularly,In the time that quantum point grain diameter increases, can make the wavelength of fluorescent emission higher, in the time that particle diameter reduces, can makeThe wavelength of fluorescent emission is lower. And the pH scope of application of both sexes quantum dot of the present invention is wider,In the scope of pH=1～14, the surface of quantum dot is all with electric charge, and the repulsive interaction between surface charge hindersStop the coagulation of quantum dot, therefore in the scope of pH=1～14, all there is good fluorescence property; AndAnd both sexes quantum dot good stability of the present invention, be uniformly dispersed, higher salinity can not cause quantum yetThe coagulation of point.
In addition, the invention provides both sexes quantum dot of the present invention in gene transfection, biomarker, lifeApplication on thing separation, immune detection, drug targeting release and target imaging. Both sexes of the present inventionQuantum dot is owing to having above-mentioned excellent properties, be therefore specially adapted to gene transfection, biomarker,The fields such as bio-separation, immune detection, drug targeting release and target imaging.
Below the specific embodiment of the present invention is elaborated. Should be understood that this placeThe detailed description of the invention of describing, only for description and interpretation the present invention, is not limited to the present invention.
Preparation example 1
This preparation example is for Sulfonic Gemini Surfactants of the present invention.
Get 5.4g ethylenediamine in there-necked flask, add 100mL absolute ethyl alcohol, stir lower dropping 16.4G bromododecane hydrocarbon, back flow reaction 48h at 80 DEG C; By thin-layer chromatography TLC detection reaction process,Question response removes absolute ethyl alcohol under reduced pressure after carrying out completely, obtains faint yellow solid powder; Wash gained with etherSolid several times, until faint yellow solid powder becomes white; With mixed solvent methyl alcohol-chloroform (1:2) by gainedWhite solid powder recrystallization 3 times, obtains white needles pressed powder, vacuum drying 24h, gained whiteNeedle-like solid powder is N, N '-bis-alkyl ethylenediamines. Get 3.2gN, N '-bis-alkyl ethylenediamines and 5.75g1,3-the third sultone is dissolved in 50mL methyl alcohol, and heating reflux reaction 24h under nitrogen protection, by gainedSolution decompression suction filtration obtain white solid; White solid is recrystallized with methyl alcohol-chloroform, obtains whitePressed powder, vacuum drying 24h, gained white solid powder is sulfonate type Gemini surface-activeAgent SGS, known by the analysis of infrared spectrum and nucleus magnetic hydrogen spectrum, its structure is suc as formula shown in (5),
Preparation example 2
This preparation example is for double quaternary ammonium salt type surfactant of the present invention.
Get 30.29mLN, N-dimethyl dodecyl tertiary amine and 4.31mL Bromofume, be dissolved in 150mLIsopropyl alcohol, 85 DEG C of back flow reaction 48h, remove solvent isopropyl alcohol under reduced pressure. With 150mL acetone to productBe recrystallized, obtain white solid powder, 40 DEG C of vacuum drying 24h. Products therefrom is bi-quaternary ammonium salt,Be designated as BAS, known by the analysis of infrared spectrum and nucleus magnetic hydrogen spectrum, its structural formula is suc as formula shown in (6).
Preparation example 3-6 is for the preparation of water-soluble quantum dot of the present invention.
Preparation example 3
This preparation example is modified ZnSe quantum dot for the preparation of mercaptopropionic acid (MPA).
The preparation of Zn precursor: take 0.9mmolZnCl2And 1.53mmolMPA, be dissolved in 90mLIn ultra-pure water. Dropwise add while stirring 1molL–1NaOH solution (ultra-pure water preparation) regulates pHTo 11.5. Solution is transferred in there-necked flask, adopts Schlenk technology, the inflation (high-purity Ar) of bleedingSix times repeatedly, eliminate the oxygen in solution.
The preparation of NaHSe: take 0.0632gSe powder and 0.1gNaBH4, be placed in the centrifugal of 10mLGuan Zhong, adds 2mL ultra-pure water, and under ice-water bath, stirring reaction is to colourless transparent solution.
At room temperature, under strong stirring, in Zn precursor, add freshly prepd NaHSe solution with syringe,[Zn]: [MPA]: [Se]=1:1.2:0.4. ZnSe precursor solution is added in digester, then will digestTank is placed in oil bath, and 160 DEG C are reacted 15 minutes, can obtain the ZnSe quantum dot that MPA modifies. AddEnter a certain amount of isopropyl alcohol to solution and become muddy, the centrifugal supernatant of abandoning, in triplicate. By sinking of centrifugal collectionShallow lake is placed in vacuum drying chamber, 35 DEG C of dry 48h.
Analysis by infrared spectrum and fluorescence spectrum is known, obtains MPA and modifies ZnSe quantum dot (alsoBe that MPA molecule is by himself sulfydryl and Metal Zn Se quantum dot surface conjunction). By inductance couplingClose plasma mass spectrograph and elementary analysis detect known, with respect to a described water-soluble quantum dot, tableThe number of the mercaptopropionic acid that face is modified is on average about 40. In addition, receive through Ma Erwen ZetasizerNanoRice particle size analyzer detects, and the particle diameter of the ZnSe quantum dot that prepared MPA modifies is about 5nm.
Preparation example 4
This preparation example is modified CdTe quantum dot for the preparation of MPA.
The preparation of Cd precursor: take 0.2mmolCdCl2And 0.34mmolMPA, be dissolved in 50mLUltra-pure water. Dropwise add while stirring 1molL–1NaOH solution (ultra-pure water preparation) regulates pH extremely8.0. Solution is transferred in there-necked flask, adopts Schlenk technology to bleed inflation (high-purity Ar) repeatedlySix times, eliminate the oxygen in solution.
The preparation of Te precursor: take 0.2mmolTe powder and 0.5mmolNaBH4, be placed in 10mL'sIn centrifuge tube, add 2mL ultra-pure water, stirring reaction under ice-water bath is until become colourless transparent solution.
At room temperature, under strong stirring, in Cd precursor, add 0.4mL freshly prepd with syringeNaHTe solution (0.04mmol), [Cd]: [MPA]: [Te]=1:1.7:0.2. There-necked flask is placed inIn oil bath, condensing reflux obtains the CdTe quantum dot that MPA modifies for 2 hours.
Analysis by infrared spectrum and fluorescence spectrum is known, obtains MPA and modifies CdTe quantum dot (alsoBe that MPA molecule is by himself sulfydryl and metal CdTe quantum dot surface conjunction). By inductance couplingClose plasma mass spectrograph and elementary analysis detect known, with respect to a described water-soluble quantum dot, tableThe number of the mercaptopropionic acid that face is modified is on average about 52. In addition, receive through Ma Erwen ZetasizerNanoRice particle size analyzer detects, and the particle diameter of the CdTe quantum dot that prepared MPA modifies is about 5nm.
Preparation example 5
This preparation example is modified CdTe/ZnS quantum dot for the preparation of MPA.
By 1mmolZnCl2、0.2mmolNa2S and 5mmolMPA solution and back gained CdTeQuantum dot is mixed into 40mL precursor solution, dropwise adds 1molL in the time stirring–1NaOH solution,Regulate pH11.0, control [Zn]: [MPA]: [S]=1:5:0.2, logical nitrogen 30 minutes is to remove as far as possibleOxygen in solution to the greatest extent. By reactant mixture be heated to 65 DEG C reaction within 3 hours, obtain MPA modifyCdTe/ZnS core/shell structure quantum dot.
Analysis by infrared spectrum and fluorescence spectrum is known, obtains MPA and modifies CdTe/ZnS quantum dot(being also that MPA molecule is by himself sulfydryl and metal CdTe/ZnS quantum dot surface conjunction). LogicalCross icp ms and elementary analysis detect known, with respect to a described water-soluble amountSub-, the number of the mercaptopropionic acid of finishing is on average about 54. In addition, through Ma Erwen ZetasizerNano nano particle size instrument detects, and the particle diameter of the CdTe/ZnS quantum dot that prepared MPA modifies is about8nm。
Preparation example 6
This preparation example is modified Ag for the preparation of MPA2S quantum dot, is designated as AS.
10mL ethylene glycol is placed in to there-necked flask, passes into after Ar air-flow exhaust 30min, be warming up to110 DEG C, add while stirring 100 μ LMPA, then by 0.05mmolAgNO3Join reaction moltenIn liquid. Be warming up to 150 DEG C. When after reaction 15 minutes, stop stirring and heating, reaction solution is coolingTo room temperature, add ultra-pure water, centrifugal after solution muddiness, the Ag that MPA modifies2S quantum dot.
Analysis by infrared spectrum and fluorescence spectrum is known, obtains MPA and modifies Ag2S quantum dot (alsoBe that MPA molecule is by himself sulfydryl and metal A g2S quantum dot surface conjunction). By inductance couplingClose plasma mass spectrograph and elementary analysis detect known, with respect to a described water-soluble quantum dot, tableThe number of the mercaptopropionic acid that face is modified is on average about 24. In addition, receive through Ma Erwen ZetasizerNanoRice particle size analyzer detects, the Ag that prepared MPA modifies2The particle diameter of S quantum dot is about 2nm.
Following examples are used for illustrating that the present invention is by quaternary cationic surfactant and anionicThe surfactant modified method on water-soluble quantum dot surface of Gemini, and the both sexes that prepareQuantum dot.
Embodiment 1
1) get the ZnSe quantum dot that MPA prepared by preparation example 3 modifies and be dissolved in ultra-pure water, quantum dotThe concentration of the aqueous solution is 100 μ molL-1. Getting in addition 6 μ L lauryl mercaptans is dissolved in 5mL acetone and makesLauryl mercaptan solution. In gained lauryl mercaptan solution, drip fast above-mentioned quantum dot aqueous solution 5mL(1min dropwises), then strong stirring 24h (mixing speed is about 250r/min) at 25 DEG C.
2) by step 1) gained mixture removes solvent to 5 μ L under reduced pressure, then adds 5mL toluene alsoUltrasonic dispersion.
3) to step 2) add preparation example 1 prepared SGS water-soluble of 5mL in gained mixture(concentration is 240 μ molL to liquid-1), the mol ratio that makes SGS and quantum dot is 2.4:1, then willGained mixture is DEG C strong stirring 24h (mixing speed is about 250r/min) at approximately 45 DEG C. Leave standstill and treatAfter layering, discard toluene layer. After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS buffer solution (pH=7.4) dialysis.
4) in the quantum dot aqueous solution (5mL) after dialysis, then add 5mL preparation example 2 to make(concentration is 252 μ molL to Bis-quaternary Ammonium Salt Surfactant BAS-1), make the electric charge of SGS and BASThan being about 1.05:1, then by gained mixture DEG C strong stirring 24h (mixing speed at approximately 45 DEG CBe about 250r/min). After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS buffer solution (pH=7.4) dialysis, obtains both sexes quantum dot, is designated as I1.
Analysis by infrared spectrum is known, and lauryl mercaptan is connected to metal by the sulfydryl of himselfThe surface of ZnSe quantum dot, and the chain alkyl of lauryl mercaptan respectively with chain alkyl and the BAS of SGSChain alkyl combine by hydrophobic interaction.
Embodiment 2
1) get the CdTe quantum dot that MPA prepared by preparation example 4 modifies and be dissolved in ultra-pure water, quantum dotThe concentration of the aqueous solution is 80 μ molL-1. Getting in addition 8 μ L lauryl mercaptans is dissolved in 7mL acetone and makes tenTwo thiol solutions. In gained lauryl mercaptan solution, drip fast above-mentioned quantum dot aqueous solution 7mL(1.5min dropwises), then strong stirring 24h (mixing speed is about 250r/min) at 25 DEG C.
2) by step 1) gained mixture removes solvent to 5 μ L under reduced pressure, then adds 7mL toluene alsoUltrasonic dispersion.
3) to step 2) add preparation example 1 prepared SGS water-soluble of 7mL in gained mixture(concentration is 160 μ molL to liquid-1), the mol ratio that makes SGS and quantum dot is 2.0:1, then willGained mixture is DEG C strong stirring 24h (mixing speed is about 250r/min) at approximately 45 DEG C. Leave standstill and treatAfter layering, discard toluene layer. After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS buffer solution (pH=7.4) dialysis.
4) in the quantum dot aqueous solution (7mL) after dialysis, then add 7mL dodecyl trimethyl(concentration is 176 μ molL to ammonium bromide (DTAB)-1), the charge ratio of SGS and DTAB is about1.1:1, then by gained mixture at approximately 45 DEG C a DEG C strong stirring 24h (mixing speed is about250r/min). After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS is slowRush liquid (pH=7.4) dialysis, obtain both sexes quantum dot, be designated as I2.
Analysis by infrared spectrum is known, and lauryl mercaptan is connected to metal by the sulfydryl of himselfThe surface of CdTe quantum dot, and the chain alkyl of lauryl mercaptan respectively with chain alkyl and the BAS of SGSChain alkyl combine by hydrophobic interaction.
Embodiment 3
1) get the CdTe/ZnS quantum dot that MPA prepared by preparation example 5 modifies and be dissolved in ultra-pure water, amountThe concentration of the son point aqueous solution is 120 μ molL-1. Getting in addition 10 μ L lauryl mercaptans is dissolved in 8mL acetoneMake lauryl mercaptan solution. In gained lauryl mercaptan solution, drip fast above-mentioned quantum dot aqueous solution 8mL(2min dropwises), then strong stirring 24h (mixing speed is about 250r/min) at 25 DEG C.
2) by step 1) gained mixture removes solvent to 5 μ L under reduced pressure, then adds 8mL benzo superSound disperses.
3) to step 2) add preparation example 1 prepared SGS water-soluble of 8mL in gained mixture(concentration is 204 μ molL to liquid-1), the mol ratio that makes SGS and quantum dot is 1.7:1, then willGained mixture is DEG C strong stirring 24h (mixing speed is about 250r/min) at approximately 45 DEG C. Leave standstill and treatAfter layering, discard toluene layer. After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS buffer solution (pH=7.4) dialysis.
4) in the quantum dot aqueous solution (8mL) after dialysis, then add 8mL dodecyl trimethyl(concentration is 220 μ molL to ammonium chloride (DTAC)-1), the charge ratio of SGS and DTAC is about1.08:1, then by gained mixture at approximately 45 DEG C a DEG C strong stirring 24h (mixing speed is about 250R/min). After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS bufferingLiquid (pH=7.4) dialysis, obtains both sexes quantum dot, is designated as I3.
Analysis by infrared spectrum is known, and lauryl mercaptan is connected to metal by the sulfydryl of himselfThe surface of CdTe/ZnS quantum dot, and the chain alkyl of lauryl mercaptan respectively with the chain alkyl of SGS andThe chain alkyl of BAS combines by hydrophobic interaction.
Embodiment 4
1) get the Ag that MPA prepared by preparation example 6 modifies2S quantum dot is dissolved in ultra-pure water, quantum dotThe concentration of the aqueous solution is 100 μ molL-1. Get in addition 6 μ L n-hexadecyl mercaptan and be dissolved in 5mL acetoneIn make lauryl mercaptan solution. In gained lauryl mercaptan solution, drip fast the above-mentioned quantum dot aqueous solution5mL (1min dropwises), then strong stirring 24h (mixing speed is about 250r/min) at 25 DEG C.
2) by step 1) gained mixture removes solvent to 5 μ L under reduced pressure, then adds 5mL chloroform alsoUltrasonic dispersion.
3) to step 2) add preparation example 1 prepared SGS water-soluble of 5mL in gained mixture(concentration is 220 μ molL to liquid-1), the mol ratio that makes SGS and quantum dot is 2.2:1, then willGained mixture is DEG C strong stirring 24h (mixing speed is about 250r/min) at approximately 45 DEG C. Leave standstill and treatAfter layering, discard toluene layer. After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS buffer solution (pH=7.4) dialysis.
4) in the quantum dot aqueous solution (5mL) after dialysis, then add 5mL cetyl trimethyl(concentration is 246 μ molL to ammonium bromide (CTAB)-1), the charge ratio of SGS and CTAB is about1.12:1, then by gained mixture at approximately 45 DEG C a DEG C strong stirring 24h (mixing speed is about250r/min). After above-mentioned solution is filtered with 0.22 μ m filtering head, with 1 × 10-2mol·L-1PBS is slowRush liquid (pH=7.4) dialysis, obtain both sexes quantum dot, be designated as I4.
Analysis by infrared spectrum is known, and n-hexadecyl mercaptan is connected to gold by the sulfydryl of himselfBelong to Ag2The surface of S quantum dot, and the chain alkyl of n-hexadecyl mercaptan respectively with the long-chain alkane of SGSThe chain alkyl of base and BAS combines by hydrophobic interaction.
Embodiment 5
Carry out according to the method for embodiment 1, difference is that the addition sequence of SGS and BAS is adjustedChange, in step 3) in add BAS, in step 4) in add SGS. Finally obtain both sexes quantumPoint, is designated as I5.
Analysis by infrared spectrum is known, and n-hexadecyl mercaptan is connected to gold by the sulfydryl of himselfBelong to the surface of ZnSe quantum dot, and the chain alkyl of lauryl mercaptan respectively with the chain alkyl of SGS andThe chain alkyl of BAS combines by hydrophobic interaction.
Comparative example 1
Carry out according to the method for embodiment 1, difference is, the MPA directly being prepared by preparation example 3The ZnSe quantum dot solid of modifying adds in 5mL toluene and ultrasonic dispersion. Found that this water-soluble amountSub-point cannot be dispersed in toluene, can not get the organic solution of water-soluble quantum dot, therefore cannot continueContinuous step below, thus cannot make both sexes quantum dot.
Test case
Both sexes quantum dot I1～I6 that embodiment 1-6 and comparative example 1 are prepared and D1 are according to belowMethod is tested, and result is remembered in table 1.
(1) electron microscope photo scanning: the both sexes quantum dot I3 that embodiment 3 is prepared carries out Electronic Speculum and sweepsRetouch, acquired results is shown in Fig. 1, and as can be seen from Figure 1, quantum dot is approximate spherical in shape, distribution of sizes phaseTo more concentrated, favorable dispersibility, lattice fringe is clear.
(2) particle diameter: use Ma Erwen ZetasizerNano nano particle size instrument to detect, acquired results is in Table1。
(3) fluorescent emission wavelength: use LS-55 XRF (U.S., PE company) to detect,Acquired results is in table 1; In addition, I1～I4 embodiment 1-4 being made is that representative is by their fluorescence spectrumFigure is plotted in Fig. 2, and the quantum dot fluorescence emission peak symmetry preparing is as can be seen from Figure 2 differentThe fluorescent emission wavelength of quantum dot can cover the scope of 370-800nm, and therefore the present invention is by selecting notSame quantum dot, fluorescent emission can realize at 370-800nm adjustable.
(4) impact of pH on fluorescence intensity: by add 1molL in quantum dot solution-1HCl orPerson NaOH regulates pH, use LS-55 XRF instrument (U.S., PE company) working sampleFluorescence intensity. CdTe/ZnS quantum dot and embodiment 3 that the MPA making with preparation example 5 modifies makeBoth sexes quantum dot I3 be example, the result recording is plotted in Fig. 3. As can be seen from Figure 3, pass throughUse method of the present invention anion and cationic surfactant to be modified to the table of water-soluble quantum dotFace, the both sexes quantum dot that can make gained arrive is more stable, all has excellent in the scope of pH=1～14Good fluorescence property; And it is more unstable to modify previous water-soluble quantum dot, in the time that pH is lower, send outGiven birth to fluorescent quenching, the pH scope of application is narrow.
(5) impact of cell culture medium on fluorescence intensity: get a certain amount of quantum dot solution, addIn DMEM cell culture medium, place different time, use respectively LS-55 XRF instrument (U.S.State, PE company) fluorescence intensity of working sample. The MPA making with preparation example 5 modifiesThe both sexes quantum dot I3 that CdTe/ZnS quantum dot and embodiment 3 make is example, and the result recording is plotted inIn Fig. 4. As can be seen from Figure 4, the method for the application of the invention is lived anion and cationic surfaceThe surface of water-soluble quantum dot is modified in property agent, can make gained to both sexes quantum dot cultivate at cellMore stable in base, there is more good performance.
(6) quantum yield (%): use respectively TU-1900 ultraviolet-visible spectrophotometer and LS-55 glimmeringPhotothermal spectroscopic analyzer, uv-visible absorption spectra and the fluorescence emission spectrum of mensuration quantum dot solution. With Luo DanBright 6G be reference (exception be that ZnSe quantum dot is with quinoline sulfate (0.1molL-1H2SO4Solution)For reference), measure the quantum yield that synthesizes gained quantum dot solution. Assay method is as follows: preparation one isThe quantum dot solution of row variable concentrations and rhodamine 6G solution, measure above-mentioned solution in excitation wave strong pointAbsorbance (absorbance is no more than 0.1) and fluorescence emission spectrum. By the fluorescence peak in fluorescence emission spectrumPeak area is mapped to absorbance, after linear fit, can obtain slope. According to formula (7), can the amount of trying to achieve by slopeSub-productive rate:
Φ X = Φ S T ( Grad X Grad S T ) ( η X 2 η S T 2 ) Formula (7).
In formula: ΦXAnd ΦSTIt is respectively the quantum of testing sample (quantum dot) and reference (rhodamine 6G)Productive rate; GradXAnd GradSTRespectively the glimmering of testing sample (quantum dot) and reference (rhodamine 6G)The slope of photopeak area to absorbance; η is the refractive index of solvent.
(7) in conjunction with effect: the detection through icp ms and elementary analysis canObtain, with respect to a described water-soluble quantum dot, with the alkyl hydrosulfide of water-soluble quantum dot finishingLive in mean number, the anionic type Gemini surface surface of the quaternary cationic surfactant combiningProperty agent mean number, and the mean number of the alkyl hydrosulfide of water-soluble quantum dot finishing, as tableShown in 1.
Table 1
Can find out from the result of test, the method according to this invention can be by quaternaries cation surfaceActive agent molecule and anionic type Gemini surface active agent molecule directly and water-soluble quantum dot surface repairThe alkyl hydrosulfide that the carbon number of decorations is 8-18 combines, and the method process simply, easily operates and becomesThis is cheap, and the quantum yield of gained is relatively high in the art. And, both sexes amount of the present inventionThe particle diameter of son point can be controlled in the scope of 1-15nm, and fluorescent emission can within the scope of 370-800nmAdjust, good stability, is uniformly dispersed, and all has good fluorescence property in the scope of pH=1～14.
Both sexes quantum point grain diameter of the present invention is less, and quantum yield is high, can in cell culture fluid, stablizeExist, can within the scope of wider pH, use. Therefore, quantum dot of the present invention is as gene transfectionCarrier, biomarker probe, immune detection probe, drug targeting release vehicle and cell imaging are visitedPin uses, and has more excellent, stable performance.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentionedDetail in embodiment, within the scope of technical conceive of the present invention, can be to skill of the present inventionArt scheme is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention. In additionIt should be noted that, each the concrete technical characterictic described in above-mentioned detailed description of the invention, notIn the situation of contradiction, can combine by any suitable mode, for fear of unnecessary weightMultiple, the present invention is to the explanation no longer separately of various possible combinations. In addition, of the present invention variousBetween same embodiment, also can be combined, as long as it is without prejudice to thought of the present invention, itsShould be considered as equally content disclosed in this invention.

Claims (13)

1. a both sexes quantum dot, is characterized in that, this both sexes quantum dot is taking water-soluble quantum dot as baseBody, this water-soluble quantum dot surface is at least modified with the alkyl hydrosulfide that carbon number is 8-18, and this alkaneBase mercaptan combines with quaternary cationic surfactant and anionic type Gemini surface active agent,Described water-soluble quantum dot is metallic water-soluble quantum dot, and the particle diameter of described water-soluble quantum dot is1-15nm。
2. both sexes quantum dot according to claim 1, wherein, described water-soluble quantum dot isZnSe quantum dot, CdTe quantum dot, CdTe/ZnS quantum dot and Ag2One in S quantum dot or manyKind;
Preferably, with respect to a described water-soluble quantum dot, the described carbon number of finishing isThe number of the alkyl hydrosulfide of 8-18 is 20-60;
Preferably, the surface of described water-soluble quantum dot is also modified with mercaptopropionic acid, with described water-soluble amountThe total number of all molecules that contain sulfydryl of the finishing of son point is benchmark, the content of this mercaptopropionic acidBe below 10%.
3. both sexes quantum dot according to claim 1, wherein, described water-soluble with respect to oneQuantum dot, the number of the described anionic type Gemini surface active agent that combines with described alkyl hydrosulfide is5-15, is preferably 10-15, lives in the described quaternaries cation surface combining with described alkyl hydrosulfideThe charge ratio of property agent and described anionic type Gemini surface active agent is 1.01-1.15:1.
4. both sexes quantum dot according to claim 1, wherein, described quaternaries cation tableSurface-active agent is selected from bi-quaternary ammonium salt cationoid surfactant and mono-quaternaries cationoid surface-activeOne or more in agent;
Preferably, described bi-quaternary ammonium salt cationoid surfactant has structure shown in formula (1), instituteState mono-quaternaries cationoid surfactant and there is structure shown in formula (2),
In formula (1), m and n are selected from the arbitrary integer in 7-17 independently of one another, and X is halogen,In formula (2), p is selected from the arbitrary integer in 7-17, and X is halogen;
Preferably, when described quaternary cationic surfactant is bi-quaternary ammonium salt cationoid surfaceWhen activating agent, described anionic type Gemini surface active agent and quaternary cationic surfactantCharge ratio be 1.03-1.08:1, when described quaternary cationic surfactant is mono-quaternaries classWhen cationic surfactant, described anionic type Gemini surface active agent and quaternaries cationThe charge ratio of surfactant is 1.06-1.15:1.
5. both sexes quantum dot according to claim 1, wherein, described anionic type Gemini surface tableSurface-active agent is the Sulfonic Gemini Surfactants with structure shown in formula (3),
Wherein, a and b are selected from the arbitrary integer in 7-17 independently of one another, and Y is alkali metal.
6. a method of preparing both sexes quantum dot, is characterized in that, the method comprises the following steps:
1) solution of alkyl hydrosulfide and the metallicity of mercaptopropionic acid modification that carbon number is 8-18 will be containedThe aqueous solution of water-soluble quantum dot carry out the first contact, the particle diameter of described water-soluble quantum dot is1-15nm；
2) will after the product removal solvent after the first contact, be dispersed in organic solvent;
3) by the aqueous solution of quaternary cationic surfactant and anionic type Gemini surface activeOne and step 2 in the aqueous solution of agent) products therefrom carries out second and contacts, then stratification abandoningFall organic layer, gained water is dialysed for the first time and obtained the quantum dot aqueous solution;
4) by the aqueous solution of quaternary cationic surfactant and anionic type Gemini surface activeAnother kind and step 3 in the aqueous solution of agent) products therefrom carries out the 3rd and contacts, then that gained is water-solubleLiquid is dialysed for the second time.
7. method according to claim 6, wherein, in step 1) in, described the first contact bagDraw together the aqueous solution of water-soluble quantum dot is added drop-wise to and contains the solution that carbon number is the alkyl hydrosulfide of 8-18In;
Preferably, the condition of described the first contact comprises: temperature is 15-50 DEG C, and the time is 20-30h;
Preferably, the concentration of the water-soluble quantum dot in the aqueous solution of water-soluble quantum dot is50～500μmol/L；
Preferably, described in, containing alkyl hydrosulfide in the solution of alkyl hydrosulfide and the volume ratio of solvent is 1:600-1000；
Preferably, the solvent in the solution that contains alkyl hydrosulfide is acetone;
Preferably, described in, contain the body of the solution of alkyl hydrosulfide and the aqueous solution of described water-soluble quantum dotLong-pending than being 1:0.5-2.
8. method according to claim 6, wherein, in step 2) in, described organic solvent isOne or more in toluene, benzene and chloroform;
Preferably, described by the volume after the product removal solvent after the first contact and the body of organic solventLong-pending than being 1:800-2000;
Preferably, described in, be separated into ultrasonic dispersion.
9. method according to claim 6, wherein, described water-soluble quantum dot and described the moon fromThe mol ratio of subtype Gemini surfactant is 1:1-3, is preferably 1:1.7-2.4;
Preferably, in step 3) in, the condition of described the second contact comprises: temperature is 30-60 DEG C,Time is 20-30h;
Preferably, in step 4) in, the condition of described the 3rd contact comprises: temperature is 30-60 DEG C,Time is 20-30h;
Preferably, the concentration of the aqueous solution of described quaternary cationic surfactant is80-1200μmol·L-1, the concentration of the aqueous solution of described anionic type Gemini surface active agent is80-1200μmol·L-1。
10. according to the method described in any one in claim 6-9, wherein, described water-soluble quantumThe particle diameter of point is 2-10nm.
Preferably, with respect to a described water-soluble quantum dot, the number of the mercaptopropionic acid of finishing is20-60；
Preferably, described water-soluble quantum dot is ZnSe quantum dot, the mercaptopropionic acid that mercaptopropionic acid is modifiedThe CdTe quantum dot of modifying, the CdTe/ZnS quantum dot that mercaptopropionic acid is modified and mercaptopropionic acid are modifiedAg2One or more in S quantum dot.
11. according to the method described in any one in claim 6-9, wherein, and described quaternary ammonium salt sunIonic surface active agent is selected from bi-quaternary ammonium salt cationoid surfactant and mono-quaternaries cationoid tableOne or more in surface-active agent;
Preferably, described bi-quaternary ammonium salt cationoid surfactant has structure shown in formula (1), instituteState mono-quaternaries cationoid surfactant and there is structure shown in formula (2),
In formula (1), m and n are selected from the arbitrary integer in 7-17 independently of one another, and X is halogen,In formula (2), p is selected from the arbitrary integer in 7-17, and X is halogen;
Preferably, when described quaternary cationic surfactant is bi-quaternary ammonium salt cationoid surfaceWhen activating agent, described anionic type Gemini surface active agent and quaternary cationic surfactantCharge ratio be 1.03-1.08:1, when described quaternary cationic surfactant is mono-quaternaries classWhen cationic surfactant, described anionic type Gemini surface active agent and quaternaries cationThe charge ratio of surfactant is 1.06-1.15:1
Preferably, described anionic type Gemini surface active agent is for having the sulphur of structure shown in formula (3)Hydrochlorate type Gemini surfactant,
Wherein, a and b are selected from the arbitrary integer in 7-17 independently of one another, and Y is alkali metal.
The both sexes quantum dot that method in 12. claim 6-11 described in any one prepares.
Both sexes quantum dot in 13. claim 1-5 and 12 described in any one is in gene transfection, lifeApplication on substance markers, bio-separation, immune detection, drug targeting release and target imaging.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110171806A (en) * 2019-05-08 2019-08-27 桂林理工大学 A kind of preparation method of water solubility feux rouges sulphur quantum dot
CN110724412A (en) * 2019-10-12 2020-01-24 纳晶科技股份有限公司 Printing method of quantum dot ink
CN111087011A (en) * 2019-12-16 2020-05-01 上海电力大学 Preparation method of silver sulfide quantum dot and indium-silver sulfide quantum dot nano material and product thereof
TWI704108B (en) * 2019-01-23 2020-09-11 長庚醫療財團法人基隆長庚紀念醫院 Method for preparing water-soluble quantum dots
CN112067601A (en) * 2020-08-05 2020-12-11 武汉生之源生物科技股份有限公司 Alkaline phosphate enzymatic chemiluminescence substrate reinforcing agent and application thereof
CN113130791A (en) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 Composite material and preparation method thereof, light-emitting diode and preparation method
CN113130826A (en) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 Composition, preparation method thereof and light-emitting diode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003728A (en) * 2006-12-22 2007-07-25 华中师范大学 Water-soluble quantum point under condition of phase transition, and preparation method
CN103361067A (en) * 2013-07-16 2013-10-23 天津大学 Water-soluble quantum dot fluorescent nanosphere and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003728A (en) * 2006-12-22 2007-07-25 华中师范大学 Water-soluble quantum point under condition of phase transition, and preparation method
CN103361067A (en) * 2013-07-16 2013-10-23 天津大学 Water-soluble quantum dot fluorescent nanosphere and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HAIBING LI，ET AL.: "Single quantum dot-micelles coated with gemini surfactant for selective recognition of a cation and an anion in aqueous solutions", 《SENSORS AND ACTUATORS B: CHEMICAL》 *
JENIFER RUBIO,ET AL.: "Photoluminescence of CdSe/ZnS core-shell quantum dots stabilized in water with a pseudopeptidic gemini surfactant", 《NANOSCALE》 *
王晓琼: "双子表面活性剂修饰量子点的合成及其性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (10)

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CN110171806A (en) * 2019-05-08 2019-08-27 桂林理工大学 A kind of preparation method of water solubility feux rouges sulphur quantum dot
CN110171806B (en) * 2019-05-08 2022-04-22 桂林理工大学 Preparation method of water-soluble red light sulfur quantum dots
CN110724412A (en) * 2019-10-12 2020-01-24 纳晶科技股份有限公司 Printing method of quantum dot ink
CN111087011A (en) * 2019-12-16 2020-05-01 上海电力大学 Preparation method of silver sulfide quantum dot and indium-silver sulfide quantum dot nano material and product thereof
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CN113130826A (en) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 Composition, preparation method thereof and light-emitting diode
CN113130826B (en) * 2019-12-31 2023-08-25 Tcl科技集团股份有限公司 Composition, preparation method thereof and light-emitting diode
CN112067601A (en) * 2020-08-05 2020-12-11 武汉生之源生物科技股份有限公司 Alkaline phosphate enzymatic chemiluminescence substrate reinforcing agent and application thereof
CN112067601B (en) * 2020-08-05 2022-04-22 武汉生之源生物科技股份有限公司 Alkaline phosphate enzymatic chemiluminescence substrate reinforcing agent and application thereof

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