CN106832341A - A kind of fluorescence chitin hydrogel and its preparation method and application - Google Patents
A kind of fluorescence chitin hydrogel and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of fluorescence chitin hydrogel and its preparation method and application, belong to hydrogel field.The preparation method includes:Fluorescent material, chitin are mixed with the first mixed solution, wherein the first mixed solution is the aqueous solution that alkali and the first urea are mixed, the second mixed solution is obtained;Then, the second mixed solution is carried out into freezing processing, the second mixed solution is well mixed with crosslinking agent again after defrosting, stand solidification.The method can use multiple fluorescent substance, universality is good, obtained fluorescence chitin hydrogel can send fluorescence under ultraviolet excitation, the fluorescence is stablized relatively, and this fluorescence chitin hydrogel has good biocompatibility, safe can be applied in bio-imaging or fluoroimmunoassay field as the fluorescence imaging reagent in organism.
Description
Technical field
The present invention relates to hydrogel field, in particular to a kind of fluorescence chitin hydrogel and preparation method thereof and
Using.
Background technology
Chitin is one of most abundant natural polymer of content on the earth, because chitin has certain biological work(
Can, thus chitin is increasingly noticeable in technical field of biological material research and application.Hydrogel is by three-dimensional hydrophilic high score
Sub-network is constituted, and its structure constitutes tissue similar to macromolecular, thus has obtained widely studied in biomedical sector.
Rare earth element has the characteristics such as light, electricity, magnetic because of the particularity of its electronic structure.Early in early sixties, people
Just start for small molecule rare earth compound to be incorporated into polymerization with doping way using properties such as the distinctive light of rare earth ion, electricity, magnetic
In thing, and thereby is achieved some macromolecular materials that there is specific function and there is practicality.Afterwards, scientists by
Rare earth doped rare earth/the macromolecule for being used to obtain the properties such as the light with unexpected effect, electricity, magnetic in macromolecular material
Composite.
At present, report also not in terms of fluorescence chitin hydrogel, thus prepare a kind of novel fluorescence chitin
Hydrogel has important Research Significance and value.
The content of the invention
The first object of the present invention is to provide a kind of fluorescence chitin hydrogel, and this fluorescence chitin hydrogel is in purple
Outer light is excited down can send fluorescence, and the fluorescence is stablized relatively, and this fluorescence chitin hydrogel no cytotoxicity.
The second object of the present invention is to provide a kind of preparation method of fluorescence chitin hydrogel, and the method can be used
Multiple fluorescent substance, universality is good, and the fluorescence intensity of obtained fluorescence chitin hydrogel is big, good stability.
The third object of the present invention is to provide a kind of fluorescence chitin hydrogel in bio-imaging or fluoroimmunoassay
The application in field.This fluorescence chitin hydrogel has good biocompatibility, can safety as in organism
Fluorescence imaging reagent.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme:
A kind of preparation method of fluorescence chitin hydrogel, it includes:
Fluorescent material, chitin are mixed with the first mixed solution, wherein the first mixed solution is that alkali and the first urea are mixed
The aqueous solution for closing, obtains the second mixed solution;Then, the second mixed solution is carried out into freezing processing, again by after defrosting
Two mixed solutions are well mixed with crosslinking agent, stand solidification.
A kind of fluorescence chitin hydrogel, is obtained using the preparation method of above-mentioned fluorescence chitin hydrogel.
A kind of application of fluorescence chitin hydrogel in bio-imaging or fluoroimmunoassay field.
Compared with prior art, beneficial effects of the present invention are:
This method for preparing fluorescence chitin hydrogel, fluorescent material is uniformly distributed in chitin, is formed in
The chitin hydrogel of fluorescence can be sent under ultraviolet excitation, and can be by adjusting the fluorescent material that mix with chitin
Measure to adjust the fluorescence intensity of fluorescence chitin hydrogel.Fluorescence chitin hydrogel obtained by this method it is molten
Swollen rate is high, fluorescence is stablized relatively, fluorescence intensity is adjustable, and no cytotoxicity, with good biocompatibility, can safety
Bio-imaging or fluoroimmunoassay field are applied to as fluorescence imaging reagent in organism.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described.
Fig. 1 is the chitin hydrogel (a) that fluorescence chitin hydrogel (b) that embodiment 5 is provided is provided with comparative example 1
Comparison diagram;
Fig. 2 is the fluorescence spectra of the fluorescence chitin hydrogel that embodiment 5 is provided;
Fig. 3 is the fluorescence spectra of the fluorescence chitin hydrogel that embodiment 6 is provided;
Fig. 4 is the fluorescence spectra of the fluorescence chitin hydrogel that embodiment 7 is provided.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
Present embodiment provides a kind of preparation method of fluorescence chitin hydrogel, and it includes:
Fluorescent material, chitin are mixed with the first mixed solution, wherein the first mixed solution is that alkali and the first urea are mixed
The aqueous solution for closing, obtains the second mixed solution;Then, the second mixed solution is carried out into freezing processing, again by after defrosting
Two mixed solutions are well mixed with crosslinking agent, stand solidification.
This method for preparing fluorescence chitin hydrogel, fluorescent material is uniformly distributed in chitin, is formed in
The chitin hydrogel of fluorescence can be sent under ultraviolet excitation, and can be by adjusting the fluorescent material that mix with chitin
Measure to adjust the fluorescence intensity of fluorescence chitin hydrogel.Fluorescence chitin hydrogel obtained by this method it is molten
Swollen rate is high, fluorescence is stablized relatively, fluorescence intensity is adjustable, and no cytotoxicity, with good biocompatibility.
Further, the content of the first urea in the first mixed solution is 2~6wt%;Alkali in first mixed solution
It is NaOH or KOH, preferably NaOH, the content of alkali is 8~12wt% in the first mixed solution.Alkali in first mixed solution
With the first urea, chitin abundant dissolving at low temperature is may advantageously facilitate, so as to improve the optics of fluorescence chitin hydrogel
Transmitance and fluorescent stability.
In the preparation process of the second mixed solution, the order of addition of material is preferably:By fluorescent material be scattered in containing
In first mixed solution of alkali and the first urea, then it is mixed with chitin, obtain the second mixed solution.Due to chitin
At normal temperatures insoluble in the first mixed solution, so first fluorescent material is scattered in the first mixed solution, crust is added
Element, is conducive to improving the dispersiveness of fluorescent material, it is uniformly distributed in prepared chitin hydrogel.
Freezing processing is carried out to the second mixed solution, is conducive to being completely dissolved chitin, with further make fluorescent material with
Chitin is well mixed.Further, freezing processing include by the second mixed solution at -28~-38 DEG C freeze 8~48h, more
For preferred, freezing processing is in freezing 24h at subzero 34 DEG C by the second mixed solution.The temperature of environment where second mixed solution
It is -28~-38 DEG C to spend, and chitin can be completely dissolved, and the mixing with fluorescent material is more uniform, and mixing efficiency is high.
Add crosslinking agent in the second mixed solution after defrosting, be conducive to making the chitin molecule for being combined with fluorescent material it
Between be cross-linked with each other, formed tridimensional network.Preferably, crosslinking agent is epoxychloropropane, and its consumption is 2~6mL/100g, i.e.,
The consumption that crosslinking agent is added in the second mixed solution per 100g is 2~6mL, preferably 4mL.
In preferred embodiments of the present invention, fluorescent material is included in fluorescent RE powder, fluorescein, rhodamine and quantum dot
Any one.It is molten that fluorescent RE powder, fluorescein, rhodamine and quantum dot this four classes material can uniformly be scattered in the first mixing
In liquid, and luminous efficiency chitin hydrogel high is combined to form with chitin.
Fluorescein, also known as fluorescein, under blue light or ultraviolet irradiation, sends green fluorescence.It is (such as glimmering in various applications
Photoactivated antibody technology) in be widely used as being fluorescent tracing thing.Rhodamine, is that a kind of can be lived by the selectively staining of cell membrane
The fluorescent dye of cell mitochondrial, in yellow-green fluorescence, with fabulous biocompatibility.Quantum dot, can be carbon quantum dot,
Can also be the quantum dot of other elements, such as CdS, CdSe, CdTe, ZnSe.Quantum dot is small due to its size, is nanoscale
, make it have good fluorescent characteristic.Fluorescent RE powder, is the fluorescent material containing rare earth element.
In the present invention more preferred embodiment, fluorescent material is fluorescent RE powder, and fluorescent RE powder is at least to contain
Oxide, carbonic acid hydroxide or carbonate that two kinds of rare earth elements mutually adulterate, one kind in two kinds of rare earth elements is europium,
Cerium or terbium.
Using the fluorescent material containing at least two rare earth elements, can avoid in obtained fluorescence chitin hydrogel
Generation Fluorescence-quenching so that the fluorescence of obtained fluorescence chitin hydrogel is stablized relatively.And use two kinds of rare earth units
The mode of plain mutually doping obtains fluorescent RE powder, the stability enhancing of fluorescence.Europium, cerium or terbium these three rare earth elements are rare earths
Infrastructure elements in fluorescence three primary colours, are mutually adulterated using these three rare earth elements and other rare earth elements (such as yttrium or lanthanum),
The fluorescent RE powder of red, green, blue three primary colours can be obtained, fluorescence chitin hydrogel can be further prepared.
It is further preferred that fluorescent RE powder is the carbonic acid hydroxide at least mutually being adulterated containing two kinds of rare earth elements,
The preparation method of fluorescent RE powder is:Obtained after gadolinium nitrate is well mixed with the nitrate and the second urea of rare earth element
3rd mixed solution, 1~5h is heated by the 3rd mixed solution in 80~90 DEG C of water-bath, is then centrifuged, is washed and is done
It is dry, obtain fluorescent RE powder.
Using hydro-thermal method, it is doped rare-earth element gadolinium as main element with the nitrate of europium, cerium or terbium.When the 3rd
When being heated for 80~90 DEG C, the second urea can resolve into CO to mixed solution2And ammoniacal liquor, the nitrate reaction with rare earth element
Generate the carbonic acid hydroxide of rare earth element, as fluorescent RE powder.
Further, gadolinium nitrate and the mol ratio of the nitrate of rare earth element are 70~99 in the 3rd mixed solution:1~
30, preferably 85:15.Using in the fluorescent RE powder obtained by this ratio, gadolinium is with the mol ratio of another rare earth element
70~99:1~30, fluorescent RE powder luminous efficiency is high, fluorescent stability is strong.
Further, the nitrate of rare earth element is that the nitrate of europium nitrate or rare earth element is terbium nitrate and nitric acid
The nitrate of cerium ammonium or rare earth element is thulium nitrate and ammonium ceric nitrate.
When the nitrate of rare earth element is europium nitrate, gadolinium nitrate is doped with europium nitrate using the above method, obtained
To red fluorescence powder, its molecular formula is GdxEu1-x(OH)CO3, wherein x is 0.7~0.99.When the nitrate of rare earth element is nitre
Sour terbium and ammonium ceric nitrate, gadolinium nitrate is doped with terbium nitrate and ammonium ceric nitrate using the above method, obtains green emitting phosphor,
Its molecular formula is GdxTbyCe1-x-y(OH)CO3, wherein, x is that 0.7~0.99, y is 0.01~0.2, x+y < 1.Work as rare earth element
Nitrate be thulium nitrate and ammonium ceric nitrate, gadolinium nitrate is doped with thulium nitrate and ammonium ceric nitrate using the above method, obtain
To blue colour fluorescent powder, its molecular formula is GdxTmyCe1-x-y(OH)CO3, wherein, x is that 0.7~0.99, y is 0.01~0.2, x+y <
1。
Formed blue colour fluorescent powder and green emitting phosphor when, why be additionally added the third rare-earth element cerium, mainly by
Differed greatly with the energy level of terbium or thulium in rare-earth element gadolinium, there are larger difficulty if directly doping, it is impossible to shape
Into the fluorescent RE powder of stable performance.
A kind of fluorescence chitin hydrogel, this fluorescence chitin hydrogel is as obtained by the above method.By above-mentioned side
This fluorescence chitin hydrogel prepared by method can send fluorescence, the swelling ratio of this fluorescence hydrogel under ultraviolet excitation
High, fluorescence is stablized relatively, fluorescence intensity is adjustable, and no cytotoxicity.
A kind of application of fluorescence chitin hydrogel in bio-imaging or fluoroimmunoassay field.This fluorescence chitin
Hydrogel has good biocompatibility, can safety as fluorescence imaging reagent in organism, be widely used in biology
Imaging or fluoroimmunoassay field.
Feature of the invention and performance are described in further detail with reference to embodiments:
Embodiment 1
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
The fluorescein of 0.1g is scattered in the mixed solutions of 100g first, the NaOH containing 12wt% in the first mixed solution
With the urea of 2wt%;By the first mixed solution in ultrasonically treated 15 minutes after mechanical agitation 0.1h under 1200rpm rotating speeds, then
Chitin is added, the second mixed solution is obtained, the percent mass concentration of chitin is 2wt% in the second mixed solution;Then will
The second mixed solution for obtaining is again after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;Again by the second mixing
Solution freezes 8h at being carried out at -38 DEG C, thaw at room temperature, again by the second resulting mixed solution and epoxy after evacuation and centrifugal degassing
Chloropropane is well mixed, wherein the amount for adding epoxychloropropane is 2mL/100g solution, fluorescence chitin is obtained final product after standing solidification
Hydrogel.
Embodiment 2
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
The carbon quantum dot of 0.01g is scattered in the mixed solutions of 100g first, contains 8wt%'s in the first mixed solution
The urea of NaOH and 6wt%;By the first mixed solution in ultrasonically treated 15 minutes after mechanical agitation 1h under 1200rpm rotating speeds, with
After add chitin, obtain the second mixed solution, in the second mixed solution the percent mass concentration of chitin be 8wt%;Then
The second mixed solution that will be obtained is again after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;Second is mixed again
Close solution be carried out at -28 DEG C at freeze 48h, thaw at room temperature, after evacuation and centrifugal degassing again by the second resulting mixed solution with
Epoxychloropropane is well mixed, wherein the amount for adding epoxychloropropane is 6mL/100g solution, fluorescence first is obtained final product after standing solidification
Shell hydrogel.
Embodiment 3
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
The rhodamine of 0.05g is scattered in the mixed solutions of 100g first, contains 11wt%'s in the first mixed solution
The urea of NaOH and 4wt%;By the first mixed solution in ultrasonically treated 15 minutes after mechanical agitation 30min under 1200rpm rotating speeds,
Chitin is subsequently added, the second mixed solution is obtained, the percent mass concentration of chitin is 4wt% in the second mixed solution;So
The second mixed solution that will be obtained afterwards is again after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;Again by second
Mixed solution freezes 24h at being carried out at subzero 33 DEG C, thaws at room temperature, again that the second resulting mixing is molten after evacuation and centrifugal degassing
Liquid is well mixed with epoxychloropropane, wherein the amount for adding epoxychloropropane is 4mL/100g solution, is obtained final product after standing solidification glimmering
Light chitin hydrogel.
Embodiment 4
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
By the europkium-activated yittrium oxide (Y of 0.1g2O3:Eu) it is scattered in first mixed solution of 100g, the first mixed solution
In the NaOH containing 11wt% and 4wt% urea;By the first mixed solution in after mechanical agitation 30min under 1200rpm rotating speeds
Ultrasonically treated 15 minutes, chitin is subsequently added, obtains the second mixed solution, the percent mass of chitin in the second mixed solution
Concentration is 4wt%;Then the second mixed solution that will the be obtained mechanical agitation 30min and ultrasonically treated under 1200rpm again
After 15min;The second mixed solution is carried out at subzero 33 DEG C again freezes 24h, thawed at room temperature, again by institute after evacuation and centrifugal degassing
The second mixed solution for obtaining is well mixed with epoxychloropropane, wherein the amount for adding epoxychloropropane is 4mL/100g solution,
Red fluorescence chitin hydrogel is obtained final product after standing solidification.
Embodiment 5
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
By the gadolinium nitrate hexahydrate of 0.3373g, the europium nitrate hexahydrate of 0.0175g, the urea and 50g of 2g distillation
Water is mixed and stirred for uniformly, obtaining the 3rd mixed solution.Then by the 3rd mixed solution in 85 DEG C of water bath with thermostatic control heating 3h, heating
Room temperature cooling after end.The 3rd mixed solution is placed in a centrifuge after cooling is centrifuged, leave bottom precipitation, added suitable
The distilled water and absolute ethyl alcohol of amount carry out it is ultrasonically treated after be centrifuged again, repeat said process 4 times.It is finally that the upper strata after centrifugation is clear
Liquid falls, and bottom sediment is the fluorescent RE powder of red.
The red fluorescent RE powders of 0.1g are scattered in first mixed solution of 100g, are contained in the first mixed solution
The urea of the NaOH and 4wt% of 11wt%;By the first mixed solution at ultrasound after mechanical agitation 30min under 1200rpm rotating speeds
Reason 15 minutes, is subsequently added chitin, obtains the second mixed solution, and the percent mass concentration of chitin is in the second mixed solution
4wt%;Then the second mixed solution that will be obtained is again after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;
The second mixed solution is carried out at subzero 33 DEG C again freezes 24h, thawed at room temperature, again by resulting after evacuation and centrifugal degassing
Two mixed solutions are well mixed with epoxychloropropane, wherein the amount for adding epoxychloropropane is 4mL/100g solution, stand solidification
After obtain final product fluorescence chitin hydrogel.
The fluorescence chitin hydrogel, sends stronger feux rouges, shown in such as Fig. 1 (b) under ultraviolet light.Its swelling ratio is
73.7g/g, its fluorescence spectrum are as shown in Fig. 2 as shown in Figure 2, the maximum emission wavelength of the fluorescence chitin hydrogel is
610nm。
Embodiment 6
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
By the thulium nitrate hexahydrate of 0.180g, the ammonium ceric nitrate of 0.106g, the gadolinium nitrate hexahydrate of 1.491g, 10g
Urea and the distilled water of 250g be mixed and stirred for uniformly, obtaining the 3rd mixed solution.Then by the 3rd mixed solution at 80 DEG C
5h is heated in water bath with thermostatic control, and heating terminates rear room temperature cooling.The 3rd mixed solution is placed in a centrifuge after cooling is centrifuged, stayed
Lower bottom part is precipitated, add appropriate distilled water and absolute ethyl alcohol carry out it is ultrasonically treated after be centrifuged again, repeat said process 3 times.
Finally the supernatant liquor after centrifugation is fallen, bottom sediment is the fluorescent RE powder of blueness.
The blue fluorescent RE powders of 0.2g are scattered in first mixed solution of 100g, are contained in the first mixed solution
The urea of the NaOH and 4wt% of 11wt%;By the first mixed solution at ultrasound after mechanical agitation 30min under 1200rpm rotating speeds
Reason 15 minutes, is subsequently added chitin, obtains the second mixed solution, and the percent mass concentration of chitin is in the second mixed solution
4wt%;Then the second mixed solution that will be obtained is again after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;
The second mixed solution is carried out at subzero 33 DEG C again freezes 24h, thawed at room temperature, again by resulting after evacuation and centrifugal degassing
Two mixed solutions are well mixed with epoxychloropropane, wherein the amount for adding epoxychloropropane is 4mL/100g solution, stand solidification
After obtain final product fluorescence chitin hydrogel.
The fluorescence chitin hydrogel sends stronger blue light under ultraviolet light, and its swelling ratio is 58.6g/g, its fluorescence light
Spectrum is as shown in figure 3, from the figure 3, it may be seen that the maximum emission wavelength of the fluorescence chitin hydrogel is 415~417nm.
Embodiment 7
The present embodiment provides a kind of fluorescence chitin hydrogel, and the preparation method of the fluorescence chitin hydrogel is:
By the terbium nitrate hexahydrate of 0.178g, the ammonium ceric nitrate of 0.108g, the gadolinium nitrate hexahydrate of 1.5088g, 10g
Urea and the distilled water of 250g be mixed and stirred for uniformly, obtaining the 3rd mixed solution.Then by the 3rd mixed solution at 90 DEG C
1h is heated in water bath with thermostatic control, and heating terminates rear room temperature cooling.The 3rd mixed solution is placed in a centrifuge after cooling is centrifuged, stayed
Lower bottom part is precipitated, add appropriate distilled water and absolute ethyl alcohol carry out it is ultrasonically treated after be centrifuged again, repeat said process 5 times.
Finally the supernatant liquor after centrifugation is fallen, bottom sediment is the fluorescent RE powder of green.
The fluorescent RE powder of 0.2g greens is scattered in first mixed solution of 100g, is contained in the first mixed solution
The urea of the NaOH and 4wt% of 11wt%;By the first mixed solution at ultrasound after mechanical agitation 30min under 1200rpm rotating speeds
Reason 15 minutes, is subsequently added chitin, obtains the second mixed solution, and the percent mass concentration of chitin is in the second mixed solution
4wt%;Then the second mixed solution that will be obtained is again after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;
The second mixed solution is carried out at subzero 33 DEG C again freezes 12h, thawed at room temperature, again by resulting after evacuation and centrifugal degassing
Two mixed solutions are well mixed with epoxychloropropane, wherein the amount for adding epoxychloropropane is 4mL/100g solution, stand solidification
After obtain final product fluorescence chitin hydrogel.
The fluorescence chitin hydrogel sends stronger green glow under ultraviolet light, and its swelling ratio is 56.7g/g, its fluorescence light
Spectrum is as shown in figure 4, as shown in Figure 4, the maximum emission wavelength of the fluorescence chitin hydrogel is 505~510nm.
Comparative example 1
This comparative example provides a kind of chitin hydrogel without fluorescence, and the preparation method of the chitin hydrogel is:
The chitin of 4g is added in the first mixed solution of the urea of the NaOH containing 11wt% and 4wt%, is obtained
Second mixed solution, the percent mass concentration of chitin is 4wt% in the second mixed solution;Then the second mixing that will be obtained is molten
Liquid is after mechanical agitation 30min and ultrasonically treated 15min under 1200rpm;The second mixed solution is carried out at subzero 33 DEG C again
Freezing 12h, is thawed at room temperature, and the second resulting mixed solution is well mixed with epoxychloropropane again after evacuation and centrifugal degassing,
The amount for wherein adding epoxychloropropane is 4mL/100g solution, and chitin hydrogel is obtained final product after standing solidification.
The chitin hydrogel does not light under ultraviolet light, and such as shown in Fig. 1 (a), its swelling ratio is 100.2g/g.
Experimental example
With reference to cell experiment to fluorescence chitin hydrogel provided in an embodiment of the present invention in terms of cytotoxicity
Effect is evaluated.
Chitin hydrogel prepared by fluorescence chitin hydrogel and comparative example 1 prepared by embodiment 1-7 is entered
Row cell toxicity test.Wherein experimental group has three groups, respectively using the fluorescence chitin hydrogel prepared by embodiment 1-7;It is right
There are 1 group, the chitin hydrogel prepared by applicating ratio 1 according to group.
Specific experiment method is:
After fluorescence chitin hydrogel prepared by embodiment 1-7 is beaten into powder sample extract is prepared using autoclaving;Together
When the chitin hydrogel that comparative example 1 is provided is broken into powder after as reference extract.According to ISO10993-5 standards, press
Amount according to 200L/ holes is added to L929 cell suspending liquids in 96 orifice plates, and ensure in each hole cell density be 1 ×
104Then 96 orifice plates are placed in 37 DEG C, 5%CO by cells/ holes2In the environment of cultivate 24h.Then, change fresh medium and add
Enter sample extract (50L/ holes) after sterilizing, meanwhile, add reference extract (50L/ holes) in control group.Cell is cultivated respectively
After 24h, 48h and 72h, the MTT solution (concentration is 5mg/mL, and solvent is PBS) of 20L is added in every hole, made most
Whole MTT concentration reaches 0.5mg/mL, then 96 orifice plates is placed in incubator and places 4h under similarity condition.After removing MTT
Dimethyl sulfoxide (DMSO) is added with 150L/ hole numbers, for dissolving the first a ceremonial jade-ladle, used in libation in cell.Then, each hole is determined under 490nm wavelength
Absorbance A, and carry out calculating cell survival rate according to formula below, as a result as shown in table 1:
Cell survival rate (%)=Atest/Acontrol× 100%
In formula, AtestAnd AcontrolThe absorbance of test group and control group is represented respectively.
The cell toxicity test result of table 1.
As shown in Table 1, compared with comparative example 1, fluorescence chitin hydrogel provided in embodiment of the present invention 1-7 it is thin
Born of the same parents' life rate illustrates that the fluorescence chitin hydrogel provided in embodiment of the present invention 1-7 has good more than 90%
Biocompatibility, almost no cytotoxicity, can safety as fluorescence imaging reagent in organism be applied to bio-imaging or
Fluoroimmunoassay field.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from of the invention
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of fluorescence chitin hydrogel, it is characterised in that it includes:
Fluorescent material, chitin are mixed with the first mixed solution, wherein first mixed solution is that alkali and the first urea are mixed
The aqueous solution for closing, obtains the second mixed solution;Then, second mixed solution is carried out into freezing processing, after defrosting again
Second mixed solution is well mixed with crosslinking agent, solidification is stood.
2. the preparation method of fluorescence chitin hydrogel according to claim 1, it is characterised in that the fluorescent material bag
Include any one in fluorescent RE powder, fluorescein, rhodamine and quantum dot.
3. the preparation method of fluorescence chitin hydrogel according to claim 1, it is characterised in that the fluorescent material is
Fluorescent RE powder, the fluorescent RE powder is oxide, the carbonic acid hydroxide at least mutually being adulterated containing two kinds of rare earth elements
Or carbonate, the one kind in described two rare earth elements is europium, cerium or terbium.
4. the preparation method of fluorescence chitin hydrogel according to claim 3, it is characterised in that the fluorescent RE powder
It is the carbonic acid hydroxide at least mutually being adulterated containing two kinds of rare earth elements, the preparation method of the fluorescent RE powder is:By nitre
Sour gadolinium obtains the 3rd mixed solution after being well mixed with the nitrate and the second urea of the rare earth element, by the described 3rd
Mixed solution heats 1~5h in 80~90 DEG C of water-bath, is then centrifuged, is washed and is dried, and obtains the rare-earth fluorescent
Powder.
5. the preparation method of fluorescence chitin hydrogel according to claim 4, it is characterised in that the 3rd mixing is molten
Gadolinium nitrate described in liquid is 70~99 with the mol ratio of the nitrate of the rare earth element:1~30.
6. the preparation method of fluorescence chitin hydrogel according to claim 4, it is characterised in that the rare earth element
The nitrate is europium nitrate or for terbium nitrate and ammonium ceric nitrate or be thulium nitrate and ammonium ceric nitrate.
7. the preparation method of fluorescence chitin hydrogel according to claim 6, it is characterised in that the fluorescent RE powder
It is GdxEu1-x(OH)CO3、GdxTmyCe1-x-y(OH)CO3And GdxTbyCe1-x-y(OH)CO3In any one, wherein, x is 0.7
~0.99;Y is 0.01~0.2, x+y < 1.
8. the preparation method of fluorescence chitin hydrogel according to claim 1, it is characterised in that the freezing processing bag
Include second mixed solution in 8~48h of freezing at -28~-38 DEG C.
9. a kind of fluorescence chitin hydrogel, it is characterised in that using the fluorescence crust any one of claim 1~9
The preparation method of hydrogel is obtained.
10. a kind of fluorescence chitin hydrogel according to claim 9 is in bio-imaging or fluoroimmunoassay field
Using.
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