CN104789225B - A kind of quantum dot-silk extract gel fluorescence nano anti-fake material and preparation method thereof - Google Patents
A kind of quantum dot-silk extract gel fluorescence nano anti-fake material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the preparation of a kind of quantum dot (q μ ant μm dots, QDs) silk extract gel fluorescence nano anti-fake material, belong to field of nanometer material technology.Containing organic principle and nanocrystal in fluorescence nano anti-fake material of the present invention, described organic principle is silk extract gel, and described nanocrystal is fluorescence quantum.Described nanometer anti-fake material preparation method is first to synthesize fluorescence quantum granule, then prepares silk extract gel, is finally combined with silk extract gel by quantum dot, can be prepared by quantum dot silk extract gel nanometer anti-fake material.This nanometer anti-fake material has the advantage that good biocompatibility, fluorescence intensity are high, photoluminescent property is stable, fluorescence color is various, preparation technology is simple, be easy to detection etc., and described nanometer anti-fake material has important application prospect at the aspect such as bio-imaging, antifraud marker.
Description
Technical field
The present invention relates to a kind of quantum dot-silk extract gel composite nano materials, belong to field of nanometer material technology.
Background technology
Quantum dot (q μ ant μm dots, QD) is a kind of three-dimensional cluster, is made up of a limited number of atom, and three dimension of quantum dot are all in nanometer scale.Specifically, quantum dot is that particle diameter is less than or close to the semiconductor nano crystal grain of exciton Bohr radius, is quasiconductor transition state between molecule and crystal.It mainly has II-VI group or iii-v elementary composition, has the regular Atomic Arrangement being similar to body phase crystal.The mainly CdX (X=S, Se and Te) etc. that research at present is more.
The particle diameter of quantum dot is generally 1-10nm, owing to particle diameter is less, electronics and hole are by quantum confinement, the discrete energy levels structure with molecular characterization can be become by band continuously, fluorescence can be launched after by the excitation of certain frequency, and the composition and size by regulation and control quantum dot can strictly control its light and absorb and emission characteristic.Owing to quantum dot has unique fluorescence spectrum performance that general organic fluorescent dye is incomparable, it has caused the broad interest of life science researcher.That propose this thought the earliest is the Alivisatos group (Science of California, USA university Berkeley, 1998,281:20133-2016) and Indiana University Nie group (Science, 1998,281:2016-2018), 1998 they exist simultaneouslyScienceOn delivered respective achievement in research.Their work fully illustrates fluorescence quantum as a kind of novel biological labeling reagent, traditional organic dyestuff can be replaced completely, the fluorescence property of its excellence will bring new breakthrough for biomarker technology, and thus pull open quantum dot prelude of applied research in biotechnology.
Quantum dot is different from the feature of organic fluorescent dye as fluorescent probe and mainly shows as following 5 points:
1. there is wide excitation wavelength range, it is possible to use excite less than the exciting light of its any wavelength launching wavelength 10nm, same exciting light thus can be used simultaneously to excite multiple quantum dot, thus launch the fluorescence of different colours；And the excitation wavelength scope of organic fluorescent dye is narrower, needing the exciting light of multi-wavelength to excite multiple fluorescent dye, this can bring inconvenience to real work.
2. the emission peak of quantum dot is narrow and symmetrical, overlapping little, and quantum dot emission spectrum peak of uniform size presents Gaussian symmetric distribution；And organic fluorescent dye launches peak width and peak shape is asymmetric, and conditions of streaking is serious, brings insoluble problem to analysis detection.
3. quantum dot launch wavelength can by control nano-particle size and composition tune, therefore can needed for synthetic the quantum dot of any wavelength.
4. the fluorescence intensity of quantum dot and stability are than common high 1-2 the order of magnitude of fluorescent dye, almost without photofading phenomenon, can observe the object of institute's labelling for a long time.In the experiment of W μ etc., compare with organic dyestuff Alexa 488 labelling with quantum dot-labeled cell and find that the fluorescence of quantum dot emission is relatively strong and is difficult to be bleached.(Nat Biotechnol, 2003,21 (1): 41-46)
5. the good biocompatibility of quantum dot, especially after various chemical modifications, it is possible not only to carry out specificity coupling, little to biohazard, and biological living labelling and detection can be carried out, living cells is marked by the quantum dot such as Jaiswal, and the quantum dot probe entering cell does not affect form and the breeding of cell, cultivates the quantum dot fluorescence (Nat remaining to for 12 days see in cell
Biotechnol,2003,21(1),47-51)；And organic fluorescent dye general toxicity is relatively big, biocompatibility is poor.
The most conventional organic fluorescent dye label is mainly fluoresceins and dye stuff of rhodamine kinds.The optical characteristics of quantum dot has obvious superiority compared with traditional organic fluorescent dye, as having wide excitation spectrum, narrow emission spectrum, high fluorescence quantum yield, stable chemical nature, fluorescence lifetime length, can carry out multi-color marking etc..
By the description above with respect to quantum dot, can see that quantum dot is as a kind of novel biomarker, overcoming many deficiencies that tradition organic fluorescent dye cannot improve, be expected to become a kind of novel fluorescent probe, people have carried out more successfully exploring and attempting at biological field.Fibroin albumen is the natural polymer fibrin extracted from silkworm silk, and content accounts for the 70%-80% of silkworm silk, and containing 18 kinds of aminoacid, wherein glycine (Gly), alanine (Ala) and serine (Ser) account for more than 80% always formed.Fibroin itself has good mechanical performance and physicochemical property, such as good pliability and tensile strength, air-moisture-permeable degree, slow-releasing, degradability, harmless etc. to biology.Fibroin albumen is through CaCl2Solution or LiBr solution process, and then the self assembly of supersound process a period of time obtains silk extract gel.
Quantum dot and silk extract gel are combined and obtain a kind of novel Multifunction fluorescent nanometer anti-fake material by the present invention, and it has extraordinary application prospect at the aspect such as bio-imaging, anti-fake mark.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the invention provides a kind of good biocompatibility, fluorescence intensity is high, photoluminescent property is stable, fluorescence color is various, preparation technology is simple, be easy to quantum dot-silk extract gel fluorescence nano anti-fake material of detecting.Its concrete technical scheme is as follows:
A kind of quantum dot-silk extract gel fluorescence nano anti-fake material, containing organic principle and inorganic nano crystal grain in this material, described organic principle is silk extract gel, and described inorganic nano crystal grain is quantum dot, and described quantum dot is mainly elementary composition by II-VI group or iii-v.
Further, described quantum dot is mainly CdX, X=Te, Se and S.
Further, the silk extract gel in described material is that after the fibroin albumen process that past sericin obtains, self assembly forms by from insecticide silk, spider silk or transgenic silk.
Further, described insecticide silk is domestic silkworm silk, tussah, tussah silk, wild silk yarn, ricinus silk or alpine rush or palm-bark rain cape bag moth insecticide silk.
Further, described inorganic nano crystal grain is a kind of fluorescent nano particle, can launch fluorescence after burst of ultraviolel.
The preparation method of a kind of described quantum dot-silk extract gel fluorescence nano anti-fake material, comprises the following steps:
(1) synthesis quantum dot:
1) 50ml 3.5-5mmol/L Cd (CH is taken by graduated cylinder correct amount3COO)2Aqueous solution, pours the three-neck flask of 100ml into, is subsequently adding the TGA (TGA) of 18 μ l, regulates pH to 10.5-11.0, magnetic agitation 5-10min under room temperature with 1mol/L NaOH；
2) 50ml 0.6-1.0mmol/L K is taken by graduated cylinder correct amount2TeO3Aqueous solution, pours in above-mentioned solution, is subsequently added 80mg NaBH4, regulate pH to 10.5-11.0 with 1mol/L NaOH immediately, under room temperature, continue magnetic agitation 5-10min；
3) after reaction terminates, three-neck flask is transferred on condensing unit, launch the quantum dot of different fluorescence according to the different synthesis of condensing reflux time；
(2) preparation of silk extract gel:
1) with (0.5-1.0) wt% Na2CO3The concise cocoon layer of aqueous solution 2 times, each 30min, concise temperature 98 DEG C, bath raio is 1:(80-100)；
2) after concise the most clean with distilled water, natural drying, obtain fibroin fiber；
3) 35-50 wt%CaCl is used2Aqueous dissolution fibroin fiber, solution temperature (20-26) DEG C, the isoelectric point, IP of regulation mixed liquor is to 3.5-4.0, and bath raio is 1:(10-15).The solution obtained after dissolving pours in cellulose dialysis film (molecular cut off 12 000-14 000), and dialyse in flowing water 3d.By the solution centrifugal decontamination after dialysis, air-drying and be concentrated into 3.5-8 wt%, room temperature stands to occurring self assembly to obtain silk extract gel；
(3) quantum dot and silk extract gel is compound:
500ml is taken by graduated cylinder correct amount
2.0-4.0mg/ml silk extract gel mixes with 100ml quantum dot after purification, is subsequently adding 100 μ l 0.8-1.0mol/L Ca2+, 100W sonic oscillation 20-30 min, 8000-10000rpm
Centrifugal 3-5min, abandons supernatant, is washed with deionized twice.Obtain the complex of pure silk extract gel and quantum dot.
Further, in material formation process, addition needs to add Ca2+Just can prepare the nanometer anti-fake material fluoresced.
Further, the bivalent cation added during Material cladding is Mg2+、Sr2+、Mn2+Equally prepare fluorescent nano material.
Further, during Material cladding, C μ is added2+、Pb2+、Fe3+, the anti-fake material fluorescent quenching of preparation.
Further, because the difference of condensing reflux time can prepare the quantum dot of different-grain diameter in quantum dot building-up process；The quantum dot of the different-grain diameter anti-fake material that can obtain launch different colours fluorescence compound with silk extract gel.
The fluorescence property of quantum dot is combined by the present invention with the sustained release performance of silk extract gel, it is prepared as a kind of Multifunction fluorescent nanometer anti-fake material, the functionality advantage making the two is complementary, and the anti-fake material obtained is with a wide range of applications in terms of bio-imaging, commodity counterfeit prevention.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph one within the silk extract gel of different multiplying；
Fig. 2 is the scanning electron microscope (SEM) photograph two within the silk extract gel of different multiplying；
Fig. 3 is the quantum dot prepared according to embodiment fluorescence intensity figure under 304 nm excite.
Detailed description of the invention
As Figure 1-3, it is an object of the invention to provide a kind of preparation technology simple, photoluminescent property is excellent, stablizes the preparation method of controlled quantum dot-silk extract gel fluorescence nano anti-fake material.
The preparation technology used includes: CdTe
The synthesis in water of QDs, the preparation of silk extract gel and QDs are compound with silk extract gel.
Above-mentioned preparation scheme is specifically carried out as follows:
1) synthesis quantum dot
Cd (CH by 50 ml 4mM3COO)2Solution and the mixing of 18 μ l TGAs, under conditions of 25 DEG C, magnetic agitation is reacted 5 minutes, reaction system pH 1mol/L
NaOH is adjusted to 10.5.Take 50 ml 0.8mM K2TeO3
Add to above-mentioned reaction system, and add 80mg NaBH4, keeping system pH is 10.5, and under the conditions of 25 DEG C, magnetic agitation is reacted 5 minutes.After having reacted, 100 DEG C of water-baths, condensing reflux 1h sampling obtains fluorescence quantum sample.
2) purification of quantum dot
Mixing with dehydrated alcohol and quantum dot equal-volume, 4600rpm is centrifuged 5min, abandons supernatant, with absolute ethanol washing twice.Finally by the resuspended precipitation of water, obtain quantum dot after purification.
3) silk extract gel is prepared
With 0.8 wt% Na2CO3The concise cocoon layer of aqueous solution 2 times, each 30min, concise temperature 98 DEG C, bath raio is 1:100；After concise the most clean with distilled water, natural drying, obtain fibroin fiber；Use 40 wt%
CaCl2Aqueous dissolution fibroin fiber, solution temperature (20-26) DEG C, the isoelectric point, IP of regulation mixed liquor is to 3.5, and bath raio is 1:10；The solution obtained after dissolving pours in cellulose dialysis film (molecular cut off 14000), and dialyse in flowing water 3d.Solution after dialysis is air-dried concentration be concurrently conigenous assembling and obtain silk extract gel.
4) quantum dot and silk extract gel is compound:
500 μ l are taken by graduated cylinder correct amount
3.0 mg/ml silk extract gels and 100 μ l quantum dot mixing after purification, is subsequently adding 100 μ l 1.0mol/L Ca2+, 100W sonic oscillation 30 min, 8000rpm
Centrifugal 5min, abandons supernatant, is washed with deionized twice.Obtain pure quantum dot-silk extract gel fluorescence nano anti-fake material.
Claims (1)
1. the preparation method of quantum dot-silk extract gel fluorescence nano anti-fake material, it is characterised in that: comprise the following steps:
Synthesis quantum dot:
50ml 3.5-5mmol/L Cd (CH is taken by graduated cylinder correct amount3COO)2Aqueous solution, pours the three-neck flask of 100ml into, is subsequently adding the TGA (TGA) of 18 μ l, regulates pH to 10.5-11.0, magnetic agitation 5-10min under room temperature with 1mol/L NaOH；
50ml 0.6-1.0mmol/L K is taken by graduated cylinder correct amount2TeO3Aqueous solution, pours in above-mentioned solution, is subsequently added 80mg NaBH4, regulate pH to 10.5-11.0 with 1mol/L NaOH immediately, under room temperature, continue magnetic agitation 5-10min；
After reaction terminates, three-neck flask is transferred on condensing unit, launch the quantum dot of different fluorescence according to the different synthesis of condensing reflux time；
The preparation of silk extract gel:
1) with (0.5-1.0) wt% Na2CO3The concise cocoon layer of aqueous solution 2 times, each 30min, concise temperature 98 DEG C, bath raio is 1:(80-100)；
2) after concise the most clean with distilled water, natural drying, obtain fibroin fiber；
3) 35-50 wt%CaCl is used2Aqueous dissolution fibroin fiber, solution temperature (20-26) DEG C, the isoelectric point, IP of regulation mixed liquor is to 3.5-4.0, and bath raio is 1:(10-15)；
The solution obtained after dissolving pours into cellulose dialysis film, and cellulose dialysis retaining molecular weight is 12 000-14 000, and dialyse in flowing water 3d；
By the solution centrifugal decontamination after dialysis, air-drying and be concentrated into 3.5-8 wt%, room temperature stands to occurring self assembly to obtain silk extract gel；
Quantum dot is compound with silk extract gel:
Take 500ml 2.0-4.0mg/ml silk extract gel by graduated cylinder correct amount to mix with 100ml quantum dot after purification, be subsequently adding 100 μ l 0.8-1.0mol/L Ca2+, 100W sonic oscillation 20-30 min, 8000-10000rpm is centrifuged 3-5min, abandons supernatant, is washed with deionized twice；Obtain the complex of pure silk extract gel and quantum dot.
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