CN108084460A - A kind of cellulose/black phosphorus quantum dot composite hydrogel and preparation method thereof - Google Patents
A kind of cellulose/black phosphorus quantum dot composite hydrogel and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of cellulose/black phosphorus quantum dot composite hydrogels, which is characterized in that the composite hydrogel includes cellulose three-dimensional net structure and the black phosphorus quantum dot being supported in the cellulose three-dimensional net structure.Black phosphorus quantum dot can be steadily supported in the composite hydrogel system, it is not easy to reunite, the composite hydrogel has high photothermal conversion efficiency uniformly, stable, good with the compatibility of biological fluid, and with complete biodegradability, high biological safety, available for biomedical sector.The present invention also provides the preparation methods of the composite hydrogel.
Description
Technical field
The invention belongs to black phosphorus based nano-material preparation fields, and in particular to a kind of cellulose/black phosphorus quantum dot Compound Water
Gel and preparation method thereof.
Background technology
Black phosphorus (Black phosphorene) is a kind of new direct band gap two-dimensional material, and band gap can be from 0.3eV (this
Body state) it is adjusted to 1.5eV (individual layer) by its number of plies, it can absorb from visible ray to communication with infra-red range wavelength
Light, its higher carrier mobility, high make-to-break ratio and good photothermal conversion effect and biocompatibility, make in addition
It obtains it and shows great potential advantages in semiconductor applications, photoelectric field and biological field etc..
In biomedical sector, dispersiveness deficiency of the inorganic nano material-black phosphorus in biological fluid, it is heavy easily to occur
Drop, there are apparent geographic differences for photo-thermal effect.And the structure of current black phosphorus sill is excessively single, and black phosphorus is at it
In stability it is poor, easy separate out can not meet the targeting and persistence needed for tumor therapeutic procedure.Therefore, have
Necessity expands existence form of the black phosphorus in biomedical sector.
Cellulose is renewable resource most abundant on the earth, has complete biocompatibility, completely biodegradable etc.
Advantage, but restricted by its high crystalline and intramolecular/intermolecular hydrogen bonding, cellulose indissoluble infusibility results in difficult processing shaping,
This strongly limits development of the cellulose in bio-medical material.
The content of the invention
In consideration of it, the present invention provides a kind of cellulose/black phosphorus quantum dot composite hydrogel, black phosphorus quantum dot is in the Compound Water
High stability in gel, dispersiveness of the cellulose/black phosphorus quantum dot composite hydrogel in biological fluid is preferable, table
Reveal the excellent specific properties such as high photothermal conversion efficiency, complete biodegradability, complete biocompatibility, biological safety, and have
There is preferable mechanical strength, be expected to apply in biomedical sector.
In a first aspect, the present invention provides a kind of cellulose/black phosphorus quantum dot composite hydrogel, the composite hydrogel bags
Include cellulose three-dimensional net structure and the black phosphorus quantum dot being supported on the cellulose three-dimensional net structure.
It is weaker due to interacting between black phosphorus quantum dot, can not black phosphorus quantum dot be built by self assembly behavior
Gel, the three-dimensional net structure mainly formed in of the invention by cellulosic molecule, the cellulose is wound by black phosphorus quantum dot
In three-dimensional net structure, black phosphorus quantum dot is made to load in the system, form cellulose/black phosphorus quantum dot composite hydrogel.Its
In, the composite hydrogel significantly improves the dispersiveness of black phosphorus quantum dot, prevents the reunion between black phosphorus quantum dot.
Wherein, the three dimensional network that the cellulose three-dimensional net structure includes cellulose or cellulose derivative itself connects into
The three-dimensional net structure that network structure or cellulose and/or cellulose derivative are formed by crosslinking agent.
Wherein, the cellulose derivative includes at least one of oxidized graphene, chitosan, cyclodextrin and gelatin
Cellulose or carboxylated, the cellulose of silanization being modified.
Preferably, the crosslinking agent includes at least one of epoxychloropropane and isocyanates, but not limited to this.
Wherein, the cellulose three-dimensional net structure has the pore structure that aperture is 20-200nm.Preferably, the hole
The aperture of gap structure is 50-150nm.
Wherein, the water content of the composite hydrogel is 85%-98%.The water content of the composite hydrogel is larger, is easy to
It is dispersed in aqueous solution or organism body fluid, there is excellent compatibility with body fluid, this can improve the black phosphorus quantum dot and life
The adhesiveness of object cell and tissue.
Wherein, the size of the black phosphorus quantum dot is 1-5nm.
Wherein, the mass ratio of the cellulose in the cellulose three-dimensional net structure and black phosphorus quantum dot is 100：
(0.0001-50) is preferably 100：(0.001-10), further preferably 100：(0.001-5), more preferably 100：0.05.
In an embodiment of the present invention, the cellulose three-dimensional net structure for cellulosic molecule and cross-linking agents into
Three-dimensional net structure.
Wherein, the mass ratio of the cellulose in the cellulose three-dimensional net structure and crosslinking agent is 100：(1.372-
13.71).Preferably 100：(4.116-13.71), further preferably 100：(4.116-6.86).
Wherein, the cellulose is lignocellulosic, bamboo cellulose, lignose pulp, cotton cellulose, microcrystalline cellulose
One or more in element, hydroxyethyl cellulose, carboxymethyl cellulose.
Cellulose/black phosphorus quantum dot composite hydrogel that first aspect present invention provides, with cellulose three-dimensional network knot
Structure is carrier, and steadily load has black phosphorus quantum dot in the three-dimensional net structure, improves the dispersiveness of black phosphorus quantum dot, is prevented
Reunion between black phosphorus quantum dot, has expanded the product form of black phosphorus.The cellulose/black phosphorus quantum dot composite hydrogel exists
In biological fluid dispersiveness preferably, show high photothermal conversion efficiency, complete biodegradability, complete biocompatibility,
The excellent specific properties such as biological safety, and there is preferable mechanical strength, it is expected to apply in biomedical sector, in particular for
Therapeutic field of tumor.
Second aspect, the present invention provides a kind of preparation method of cellulose/black phosphorus quantum dot composite hydrogel, including with
Lower step：
(1) mixed solvent containing highly basic, urea and water is prepared, and carries out precooling, after cellulose powder is added to precooling
The in the mixed solvent, be vigorously stirred, obtain cellulose solution；
(2) under the conditions of high-speed stirred, black phosphorus quantum dot, crosslinking agent and the cellulose solution are mixed, at ultrasound
After reason, when progress cross-linking reaction 0.5-2 is small at 65-90 DEG C, cross-linking reaction object is obtained；
(3) add in cellulose regenerated liquid into the cross-linking reaction object and carry out immersion 30-60min, it afterwards will be after regeneration
Cross-linking reaction object, which is placed in water, dialyses, and obtains cellulose/black phosphorus quantum dot composite hydrogel.
Using cellulose made from the above method/black phosphorus quantum dot composite hydrogel, including cellulose and cross-linking agents
Into cellulose three-dimensional net structure, further include the black phosphorus quantum dot being supported in the cellulose three-dimensional net structure.Into one
Step ground, the black phosphorus quantum dot surface are covered by the cellulose three-dimensional net structure.
The crosslinking agent is preferably not exclusively hydrophobic substance.Epoxy group (C-O-C) and isonitrile are carried in the crosslinking agent
At least one of perester radical (NCO), these functional groups in so described crosslinking agent just can in the cellulose molecular chain
- OH crosslink reaction.
Preferably, one or more of the crosslinking agent in epoxychloropropane and isocyanates, but not limited to this.Into
Preferably, the crosslinking agent is epoxychloropropane to one step.At this point, hydroxy functional group (- OH) meeting and ring on cellulose molecular chain
Necleophilic reaction occurs for the carbon atom in oxygen chloropropane on epoxy-functional (C-O-C), is cross-linked to form aquogel system.
Wherein, the mixed solvent is cooled to -15~-5 DEG C in advance.So be conducive to the more preferable molten of the cellulose powder
Solution.Preferably, the mixed solvent is cooled to -12 DEG C in advance.
Optionally, the grain size of the cellulose powder is 10-30 microns.
Wherein, in step (1), the rotating speed being vigorously stirred be 7000~10000rpm, the time being vigorously stirred
For 1-3 minutes.
Wherein, in step (2), the rotating speed of the high-speed stirred is 7000~10000rpm, the time of the high-speed stirred
For 1-3 minutes.Described be vigorously stirred may be the same or different with the speed of agitator of the high-speed stirred, mixing time.
Wherein, in step (2), the power of the supersound process is 300-500W, and the time is 10-30 minutes.
Preferably, in step (2), the temperature of the cross-linking reaction is 70-85 DEG C.Such as can be 72,75,78,80 or
82℃。
Wherein, in step (3), the cellulose regenerated liquid is the dilution heat of sulfuric acid that mass fraction is 5%-10%.
Preferably, the volume ratio of the cross-linking reaction object and the dilution heat of sulfuric acid is 1：(2-3).Further, it is used
The volume of dilution heat of sulfuric acid is 10-15mL.Wherein, cross-linking reaction object for cellulose/crosslinking agent/black phosphorus quantum dot/sodium hydroxide/
The hydrogel of urea.
Wherein, in step (3), the time of the dialysis is 3-7 days.The purpose of dialysis is primarily to remove highly basic, urine
Element and regenerated liquid.
Wherein, in step (1), the in the mixed solvent, the mass concentration of highly basic is 5-15%, and the mass concentration of urea is
10-15%.
Wherein, the highly basic is the one or more in sodium hydroxide, potassium hydroxide and lithium hydroxide.
Wherein, in step (1), in the cellulose solution, the mass ratio of mixed solvent and cellulose is 100：(1-4).
Preferably, the volume of the cellulose solution and the volume ratio of the crosslinking agent are 100：(0.2-2.0).
Preferably, the mass ratio of the volume of the cellulose solution and the crosslinking agent is 100：(0.236-2.36)mL/
g。
Preferably, the mass ratio of the quality of the cellulose solution and the crosslinking agent is 100：(0.212-2.12).
Wherein, the mass ratio of the cellulose and black phosphorus quantum dot is 100：(0.0001-50).Such as can be 100：
0.01,100：0.03,100：0.05,100：0.1,100：0.5,100：1,100：5,100：10.Preferably 100：(0.001-
10) it is more preferably, 100：(0.001-5), more preferably 100：0.05.
The black phosphorus quantum dot can generate heat under near infrared light (such as 808nm) irradiation, and temperature can rise to height from room temperature
Up to 150 DEG C, by regulating and controlling its content in the composite hydrogel, required temperature (such as 43-60 for killing cancer cell can reach
DEG C), compared with other common photothermal reagents (such as nanogold, nano Pd particle, CuS and porphyrin etc.), black phosphorus quantum dot can be in life
Biodegradable behavior occurs in object, catabolite is the phosphate of security, show preferable biocompatibility and
Biological safety.
Optionally, the mass ratio of the cellulose and black phosphorus quantum dot is 100：(0.0001-0.01).At this point, institute can be made
It is 0.5/cm that composite hydrogel, which is stated, in irradiation power2808nm laser irradiation under, photo-thermal equilibrium temperature reaches 43.5-60 DEG C, can
Make the composite hydrogel irradiation power be 1.0/cm2808nm laser irradiation under, photo-thermal equilibrium temperature reaches 48-75 DEG C.
As it can be seen that during black phosphorus quantum dot containing lower quality, the light of the good killing tumor cell of the composite hydrogel can be just assigned
Thermal effect.
In the present invention, the preparation method of the black phosphorus quantum dot is unlimited, can be prepared in the following way：
It is ground, is added into grinding gained mixture described organic molten after block black phosphorus and organic solvent are mixed
Agent obtains dispersion liquid；Then under anaerobic, by the dispersion liquid when 100-160 DEG C of back flow reaction 8~24 is small, to institute
It obtains reaction solution and carries out low-speed centrifugal, collect supernatant, and solid precipitation will be collected after the supernatant high speed centrifugation, it is described solid
Body precipitation is vacuum dried, obtains the black phosphorus quantum dot.
Preferably, when the time of the reflux is 12~24 small.
Optionally, the size of the quantum dot is 1-5nm.
Optionally, the ratio between total volume of the quality of the black phosphorus and the organic solvent is (0.25-1) mg/mL.
Optionally, the time of the grinding is 20-60min, and the grinding is to carry out under anaerobic.
The surface of the organic solvent can match with the surface of two-dimentional black phosphorus, and there are certain phase interactions therebetween
The required energy of bulk black phosphorus is removed with balancing.Wherein, the organic solvent be selected from N-Methyl pyrrolidone (NMP),
In dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), n-cyclohexyl-2-pyrrolidone (CHP) and isopropanol (IPA)
One or more, but not limited to this.
Preferably, the rotating speed of the low-speed centrifugal is 5000-8000rpm, time 20-40min.It is further preferred that
The rotating speed of the low-speed centrifugal is 6000-8000rpm.
Preferably, the ultracentrifugal rotating speed is 15000-18000rpm, time 30-60min.Further preferably
Ground, the ultracentrifugal rotating speed are 16000-18000rpm.
Preferably, the vacuum drying drying temperature is 50-80 DEG C, drying time 12-24h.
The formation mechenism of cellulose provided by the invention/black phosphorus quantum dot composite hydrogel is：1) first, using hydroxide
The low-temperature alkali mixed solvent of sodium, urea and water dissolves cellulose, can by the hydrogen bond network quilt between the strand of cellulose
It is gradually opened, forms the sodium ion and hydroxide ion of hydrate, new hydrogen bond network is formed with the strand of cellulose, and urinate
Plain molecule hydrate prevents the self-association of cellulose molecular chain again, and final cellulose molecular chain is molten in the form of channel inclusion compound
Solution is dissolved in aqueous solution, which overcome high crystalline and intramolecular/intermolecular are more difficult compared with the cellulose of strong hydrogen bonding including water
The problem of usual vehicle including solvent.In addition, alkaline solution also contributes to improve the stability of black phosphorus quantum dot, protection black phosphorus
It is aoxidized to prevent it.2) when cellulose aqueous solution is mixed under high velocity agitation with black phosphorus quantum dot, crosslinking agent, ultrasound after,
Under certain temperature, necleophilic reaction occurs for cellulose molecular chain and crosslinking agent, while black phosphorus quantum dot is fitted together into, makes black phosphorus amount
Son point is in extremely stable state, forms cellulose/crosslinking agent/black phosphorus quantum dot/sodium hydroxide/urine of tridimensional network
The hydrogel of element.3) hydrogel of the cellulose/crosslinking agent/black phosphorus quantum dot/sodium hydroxide/urea is molten by dilute sulfuric acid
After the immersion of liquid, orthogenesis occurs for cellulose, i.e. precipitation phenomenon occurs for cellulose molecular chain, is taken convenient for the hydrogel after regeneration
Go out, after the immersion of water, sodium hydroxide and urea can be removed, and finally obtain cellulose/black phosphorus quantum dot composite hydrogel.
In the cellulose/black phosphorus quantum dot composite hydrogel, black phosphorus quantum dot is by steady load in cellulose and crosslinking
In the three-dimensional net structure that agent is cross-linked into, due to the obstruction of cellulose macromolecule chain, black phosphorus quantum dot is in extremely stable shape
State is not susceptible to sedimentation of reuniting so that the composite hydrogel has photo-thermal effect that is more uniform, stablizing, and photo-thermal effect is several
There is no region gender gap.Secondly, sufficient moisture is contained in the composite hydrogel, is readily dispersed in aqueous solution or biology
In body body fluid, there is excellent compatibility with body fluid, this can improve the black phosphorus quantum dot and biological cell and organize viscous
Attached property.Furthermore due to the gelation of the composite hydrogel, when as anticancer therapy system, " intratumor injection " can be passed through
Mode, be injected directly into tumor locus.In addition, the gel frame in the composite hydrogel based on cellulose may be used also
To fix other hydrophily anticancer drugs, targeted therapy, photo-thermal therapy and chemotherapy of its realization to tumour cell are assigned
Multi-mode complex treatment.Finally, due to the cellulose, black phosphorus quantum dot are degradable, good biocompatibility material,
Make the composite hydrogel that also there are the excellent specific properties such as complete biodegradability, complete biocompatibility, biological safety.
The preparation method for cellulose/black phosphorus quantum dot composite hydrogel that second aspect of the present invention provides, it is simple for process, it is green
Colour circle is protected, and products obtained therefrom is had excellent performance, stable uniform.
The advantages of embodiment of the present invention, will partly illustrate in the following description, a part according to specification be it is aobvious and
It is being clear to or can be known by the implementation of the embodiment of the present invention.
Description of the drawings
Fig. 1 is transmission electron microscope (TEM) photo of the black phosphorus quantum dot used in the embodiment of the present invention：(a) low point
Distinguish photo (scale 100nm)；(b) high-resolution pattern photo (scale 10nm).
Fig. 2 is atomic force microscope (AFM) photo of the black phosphorus quantum dot used in the embodiment of the present invention, and wherein scale is
1.0μm。
Fig. 3 is the grand of cellulose aquagel (comparative example 4) and cellulose/black phosphorus quantum dot composite hydrogel (embodiment 4)
See photo in kind.
Fig. 4 is scanning electron microscope (SEM) photo of gained aeroge after hydrogel is freeze-dried：(a) it is fiber
The corresponding aeroge of hydrogel (comparative example 4)；(b) cellulose/corresponding gas of black phosphorus quantum dot composite hydrogel (embodiment 4)
Gel.
Specific embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is unlimited
Due to following specific embodiment.In the range of constant principal right, implementation can be suitably changed.
Unless otherwise noted, raw material and other chemical reagent are all commercial goods used by the embodiment of the present invention.
Embodiment 1
A kind of preparation of cellulose/black phosphorus quantum dot composite hydrogel, including：
Step (1) prepares the black phosphorus quantum dot solid of size uniformity by liquid phase stripping method, is as follows：
1-a):Block black phosphorus and N-Methyl pyrrolidone (NMP) are added to agate by solid content ratio for 500mg/10mL
Mechanical lapping is carried out in mortar, the time is 30 minutes；Compound after grinding is moved in 100mL reaction bulbs, and adds in 90mL
NMP, obtain dispersion liquid, solid content of the final black phosphorus in total NMP is 5mg/mL.
1-b):When high temperature reflux 12 is small at 120 DEG C by above-mentioned dispersion liquid, obtain the solution of the quantum dot containing black phosphorus, i.e., it is black
The mixed solution of phosphorus quantum dot and NMP, for use.
1-c):Above-mentioned black phosphorus quantum dot solution is subjected to low-speed centrifugal, rotating speed 7000rpm, centrifugation time is 25 minutes,
It is slowly withdrawn 3/4 supernatant.
1-d):High speed centrifugation, rotating speed 17000rpm are carried out to above-mentioned supernatant, the time is 35 minutes, is slowly poured out
Clear liquid collects black phosphorus quantum dot solid.
1-e):When by above-mentioned black phosphorus quantum dot solid, drying 20 is small in vacuum drying chamber, temperature is 75 DEG C, is finally obtained
Dry black phosphorus quantum dot solid, for use.After tested, the size of gained black phosphorus quantum dot is 1-5nm.
Step (2) prepares the alkaline aqueous solution of transparent homogeneous cellulose, is as follows：
2-a):Sodium hydroxide, urea and deionized water are added to according to the ratio that mass ratio is 7%/12%/81%
In the beaker of 200mL, mixed solvent is obtained, wherein the quality of deionized water is 81.0g, i.e. the total volume of mixed solvent is
100mL；Mixed solvent is subjected to precooling 30 minutes, its temperature is made to reach -12 DEG C, for use.
2-b):Cellulose powder is added to the in the mixed solvent after above-mentioned precooling, wherein mixed solvent and cellulose
Mass ratio is 100：4；Then obtained cellulose suspension is vigorously stirred, mixing speed 7500rpm, the time 2
Minute, finally obtain homogeneous, transparent cellulose solution, i.e. the mixing of cellulose/sodium hydroxide/urea/deionized water is molten
Liquid, for use.
Step (3) prepares the composite hydrogel of cellulose/black phosphorus quantum dot, is as follows：
3-a):The cellulose solution 5mL in step (2) is taken, takes the black phosphorus quantum dot solid in step (1), wherein fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：0.0001, take epoxychloropropane 0.05mL, i.e. cellulose solution and epoxy
The ratio between volume of chloropropane is 100：1；By three's high agitation, mixing speed 7500rpm, the time is 2 minutes；Then water-bath
Ultrasound, ultrasonic power 300W, time are 15 minutes, obtain the mixed liquor after ultrasound, i.e. cellulose/epoxychloropropane/black phosphorus amount
The mixed solution of sub- point/sodium hydroxide/urea/deionized water.
3-b):Mixed liquor after above-mentioned ultrasound is placed in 70 DEG C of oil bath and carries out chemical crosslink reaction, the reaction time is
1.5 it is small when, obtain cross-linking reaction object, i.e. cellulose/epoxychloropropane/black phosphorus quantum dot/sodium hydroxide/urea/deionized water
Hydrogel.
3-c):15mL is added in into above-mentioned cross-linking reaction object, the dilution heat of sulfuric acid that mass fraction is 8%, acid soak 40 is divided
Clock, so that cellulose regenerated behavior, i.e. cellulose molecular chain is precipitated.Then, the cross-linking reaction object after regeneration is placed in
It in ionized water, dialyses 5 days, comes so that sodium hydroxide, urea, sulfuric acid gradually give, finally obtain cellulose/black phosphorus quantum dot
Composite hydrogel.
The composite hydrogel of cellulose made from the embodiment of the present invention/black phosphorus quantum dot, including cellulosic molecule and crosslinking
The three-dimensional net structure that agent is cross-linked into and the black phosphorus quantum dot being supported in the three-dimensional net structure.
Embodiment 2
The composite hydrogel of cellulose/black phosphorus quantum dot is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：0.01.
Embodiment 3
The composite hydrogel of cellulose/black phosphorus quantum dot is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：0.03.
Embodiment 4
The composite hydrogel of cellulose/black phosphorus quantum dot is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：0.05.
Embodiment 5
The composite hydrogel of cellulose/black phosphorus quantum dot is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：5.
Embodiment 6
The composite hydrogel of cellulose/black phosphorus quantum dot is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：10.
Embodiment 7
The composite hydrogel of cellulose/black phosphorus quantum dot is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus quantum dot solid is 100：50.
For prominent beneficial effects of the present invention, the present invention also provides following comparative examples：
Comparative example 1
Cellulose aquagel is prepared, including:
Step (1) first prepares the alkaline aqueous solution of transparent homogeneous cellulose, is as follows：
1-a):Sodium hydroxide, urea and deionized water are added to according to the ratio that mass ratio is 7%/12%/81%
In the beaker of 200mL, mixed solvent is obtained, wherein the quality of deionized water is 81.0g, i.e. the total volume of mixed solvent is
100mL；Mixed solvent is subjected to precooling 30 minutes, its temperature is made to reach -12 DEG C, for use.
1-b):Cellulose powder is added to the in the mixed solvent after above-mentioned precooling, wherein mixed solvent and cellulose
Mass ratio is 100：1；Then obtained cellulose suspension is vigorously stirred, mixing speed 7500rpm, the time 2
Minute, finally obtain homogeneous, transparent cellulose solution, i.e. the mixing of cellulose/sodium hydroxide/urea/deionized water is molten
Liquid.
Step (2) prepares cellulose aquagel, is as follows：
2-a):The cellulose solution 5mL in step (1) is taken, takes epoxychloropropane 0.01mL, i.e. cellulose solution and epoxy
The ratio between volume of chloropropane is 100：0.2；By three's high agitation, mixing speed 7500rpm, the time is 2 minutes；Then water
Bath ultrasound, ultrasonic power 300W, time are 15 minutes, obtain the mixed liquor after ultrasound, i.e. cellulose/epoxychloropropane/hydrogen-oxygen
Change the mixed solution of sodium/urea/deionized water, for use.
2-b):Mixed solution after above-mentioned ultrasound is placed in 70 DEG C of oil bath, chemical crosslink reaction occurs, the reaction time
For 1.5 it is small when, obtain cross-linking reaction object, i.e. the hydrogel of cellulose/epoxychloropropane/sodium hydroxide/urea/deionized water,
For use.
2-c):15mL is added in into above-mentioned cross-linking reaction object, the dilution heat of sulfuric acid that mass fraction is 8% carries out impregnating 40 points
Clock, so that cellulose regenerated behavior.Then, the cross-linking reaction object after regeneration is placed in deionized water, dialysed 5 days, so that hydrogen
Sodium oxide molybdena and urea, which gradually give, to be come, and finally obtains hydrogel (the referred to as cellulose water-setting of cellulose/epoxychloropropane
Glue).
Comparative example 2：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：2,
The ratio between volume of cellulose solution and epoxychloropropane is 100：0.4.
Comparative example 3：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：3,
The ratio between volume of cellulose solution and epoxychloropropane is 100：0.6.
Comparative example 4：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：4,
The ratio between volume of cellulose solution and epoxychloropropane is 100：1.0.
Comparative example 5：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：4,
The ratio between volume of cellulose solution and epoxychloropropane is 100：1.4.
Comparative example 6：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：4,
The ratio between volume of cellulose solution and epoxychloropropane is 100：2.0.
Fig. 1 is the transmission electron microscope microscopic appearance figure of the black phosphorus quantum dot used in the embodiment of the present invention, and (a) is
Low resolution photo；(b) it is high-resolution photo.The microscopic appearance test condition of black phosphorus quantum dot is as follows：Instrument and equipment：High-resolution is saturating
Penetrate electron microscope；Model：FEI Tecnai G2F30；Testing high voltage：300kV.
In Fig. 1 (a), the size of black phosphorus quantum dot is about about 1-3 nanometers；From Fig. 1 b, black phosphorus quantum dot is shown
It shows apparent lattice fringe, shows that the black phosphorus quantum dot in the present invention has preferable crystal structure；Its lattice dimensions is
0.223 nanometer, corresponding to (014) diffraction surfaces.
Fig. 2 is the atomic force microscopy of the black phosphorus quantum dot used in the present invention.The height map of black phosphorus quantum dot
Test condition it is as follows：Instrument and equipment：High-resolution atomic force microscope；Model：Brooker scanning probe microscopy；Scan mould
Formula：Intelligent scanning pattern.As shown in Figure 2, the thickness of these black phosphorus quantum dots is in the range of 1-5nm.
Fig. 3 provides cellulose aquagel (comparative example 4) and the macroscopic view of cellulose/black phosphorus quantum dot (embodiment 4) is in kind
Photo.From the figure 3, it may be seen that pure cellulose hydrogel (comparative example 4) is in integrally semi-transparent clear shape " jelly type " macro morphology；And
After black phosphorus quantum dot is successfully introduced into, the composite hydrogel (embodiment 4) of gained cellulose/black phosphorus quantum dot is in integrally light brown,
The two is compared with strikingly color.
Fig. 4 provides cellulose aquagel (comparative example 4) and cellulose/black phosphorus quantum dot composite hydrogel (embodiment 4)
The electron scanning micrograph of the corresponding aeroge of gained after freeze-drying.Test condition is as follows：To retain cellulose water-setting
Macromolecular porous structure in glue, hydrogel (cellulose aquagel of comparative example 4 and the cellulose/black phosphorus of embodiment 4 of test
Quantum dot composite hydrogel) it first passes around freeze-drying process and obtains corresponding aerogel structure, wherein the experiment being freeze-dried
Condition：Temperature：-80℃；Time：72 it is small when.Then the test of microscopic appearance, the instrument and equipment of use are carried out：Cold field emission is swept
Retouch electron microscope；Model：SEM-Hitachi SU8010；Test voltage：3kV；The sample surfaces silver-plated time：20 seconds.
As shown in Figure 4, this two aerogel-like shows apparent porosity, this is the three dimensional gell network by cellulose
Structure is determined.But it is significantly cellulose/epoxychloropropane produced by the present invention/black phosphorus quantum dot composite hydrogel institute
The cavernous structure distribution uniform of corresponding aeroge, aperture 50-100nm, the porosity is about 75%.
By answering for cellulose aquagel made from comparative example 1-6 and the cellulose prepared by embodiment 1-7/black phosphorus quantum dot
Heshui gel carries out Mechanics Performance Testing and light thermal property test respectively, and the results are shown in Table 1.
The basis and performance parameter of gel in table 1 comparative example 1-6 and embodiment 1-7
Table 1 gives the typical case's composition and physical property of comparative example 1-6 and embodiment 1-7 in patent of the present invention.It can by table 1
Know, in comparative example 1-6, with the raising of the volume fraction of crosslinking agent epoxychloropropane, final gained cellulose aquagel
Mechanical strength be also to significantly increase substantially.For example, when the volume ratio 100 of cellulose solution and epoxychloropropane：When 0.2
(i.e. comparative example 1), compression modulus 18.2kPa；When the volume ratio of cellulose solution and epoxychloropropane increases to 100：1
(i.e. comparative example 4) and 100：When 2 when (comparative example 6), corresponding compression modulus increases to 58.7kPa and 78.2kPa respectively,
This is because caused by more content of crosslinking agent so that the chemical crosslinking degree of cellulose aquagel greatly improves.However, pure fiber
Hydrogel lacks any functionality, does not show any photo-thermal effect, photo-thermal equilibrium temperature is 25 DEG C, with room temperature base
This is identical.
However, as striking contrast, in the Compound Water of embodiment 1-7, that is, cellulose/epoxychloropropane/black phosphorus quantum dot
In gel, due to the introducing of black phosphorus quantum dot, final photo-thermal equilibrium temperature significantly raises.For example, when cellulose with it is black
The mass ratio 100 of phosphorus quantum dot：When 0.0001 (i.e. embodiment 1), the final light thermal equilibrium temperature of composite hydrogel is in 0.5 He
1.0W/cm2When be able to reach 43.2 DEG C and 50.6 DEG C, compared with pure cellulose hydrogel, be respectively increased 18.2 DEG C and
25.6℃.When the quality point of black phosphorus quantum dot in the composite hydrogel for continuing increased fiber element/epoxychloropropane/black phosphorus quantum dot
During number, this photo-thermal equilibrium temperature significantly increases the detection range for being even more than thermal imaging system.For example, when cellulose with it is black
The mass ratio 100 of phosphorus quantum dot：When 5 (i.e. embodiment 5), the final light thermal equilibrium temperature of composite hydrogel is in 0.5 and 1.0W/
cm2When respectively 110.3 DEG C and 129.3 DEG C；When cellulose and the mass ratio 100 of black phosphorus quantum dot：10 (i.e. embodiments 6) and
100：When 50 (i.e. embodiment 7), the final light thermal equilibrium temperature of composite hydrogel has been more than the inspection of thermal imaging system higher than 150 DEG C
Survey scope.
The above result shows that the introducing of black phosphorus quantum dot not only significantly improves the mechanical strength of cellulose aquagel, and
And can actually assign cellulose aquagel excellent Photothermal characterisation, and this characteristic can by the content of black phosphorus quantum dot into
Row is adjusted.And when using the black phosphorus quantum dot of lower quality, balanced with regard to the composite hydrogel can be made to reach higher photo-thermal
Temperature.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of cellulose/black phosphorus quantum dot composite hydrogel, which is characterized in that it is three-dimensional that the composite hydrogel includes cellulose
Network structure and the black phosphorus quantum dot being supported in the cellulose three-dimensional net structure.
2. composite hydrogel as described in claim 1, which is characterized in that the cellulose three-dimensional net structure includes cellulose
Or the three-dimensional net structure that connects into of cellulose derivative itself or cellulose and/or cellulose derivative pass through crosslinking agent
The three-dimensional net structure of formation.
3. composite hydrogel as claimed in claim 1 or 2, which is characterized in that the cellulose three-dimensional net structure has hole
Footpath is the pore structure of 20-200nm.
4. composite hydrogel as claimed in claim 1 or 2, which is characterized in that the fibre in the cellulose three-dimensional net structure
The mass ratio of dimension element and black phosphorus quantum dot is 100：(0.0001-50).
5. composite hydrogel as claimed in claim 2, which is characterized in that the cellulose in the cellulose three-dimensional net structure
Mass ratio with crosslinking agent is 100：(1.372-13.71).
6. the preparation method of a kind of cellulose/crosslinking agent/black phosphorus quantum dot composite hydrogel, which is characterized in that including following step
Suddenly：
(1) prepare the mixed solvent containing highly basic, urea and water, and by its it is pre- be cooled to -15~-5 DEG C, cellulose powder is added to
The in the mixed solvent after precooling, is vigorously stirred, obtains cellulose solution；
(2) under the conditions of high-speed stirred, black phosphorus quantum dot, crosslinking agent and the cellulose solution are mixed, after supersound process,
When progress cross-linking reaction 0.5-2 is small at 65-90 DEG C, cross-linking reaction object is obtained；
(3) add in cellulose regenerated liquid into the cross-linking reaction object and carry out immersion 30-60min, afterwards by the crosslinking after regeneration
Reactant, which is placed in water, dialyses, and obtains cellulose/black phosphorus quantum dot composite hydrogel.
7. preparation method as claimed in claim 6, which is characterized in that the in the mixed solvent, the mass concentration of highly basic is 5-
15%, the mass concentration of urea is 10-15%.
8. preparation method as claimed in claim 6, which is characterized in that in the cellulose solution, mixed solvent and cellulose
Mass ratio be 100：(1-4)；The mass ratio of the quality of the cellulose solution and the crosslinking agent is 100：(0.212-
2.12)。
9. preparation method as claimed in claim 6, which is characterized in that in step (3), the cellulose regenerated liquid is quality point
Number is the dilution heat of sulfuric acid of 5%-10%；The volume ratio of the cross-linking reaction object and the dilution heat of sulfuric acid is 1：(2-3).
10. preparation method as claimed in claim 5, which is characterized in that the rotating speed of the high-speed stirred for 7000~
10000rpm, the time of the high-speed stirred is 1-3 minutes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019095753A1 (en) * | 2017-11-15 | 2019-05-23 | 深圳大学 | Cellulose/black phosphorus quantum dot composite hydrogel and preparation method therefor |
| CN110196511A (en) * | 2019-05-24 | 2019-09-03 | 武汉天马微电子有限公司 | A kind of quantum dot film and preparation method thereof, backlight module, display device |
| CN110862559A (en) * | 2019-11-29 | 2020-03-06 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-strength cellulose/bentonite composite hydrogel |
| CN111265714A (en) * | 2020-03-11 | 2020-06-12 | 四川大学 | Black phosphorus functionalized injectable hydrogel and preparation method and application thereof |
| CN112321861A (en) * | 2020-11-08 | 2021-02-05 | 天津大学 | Phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof |
| CN112903778A (en) * | 2021-02-04 | 2021-06-04 | 中南大学 | Graphene oxide-amino-beta-cyclodextrin/black phosphorus modified glassy carbon electrode and preparation method and application thereof |
| CN115068686A (en) * | 2022-05-18 | 2022-09-20 | 复旦大学附属中山医院 | Natural-source black phosphorus-silk protein-cellulose biological scaffold |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423614A (en) * | 2008-11-14 | 2009-05-06 | 武汉大学 | Luminescent fibre hydrogel and preparation method thereof |
| CN106190120A (en) * | 2016-06-30 | 2016-12-07 | 深圳先进技术研究院 | A kind of black phosphorus quantum dot and preparation method thereof |
| CN106668951A (en) * | 2016-11-23 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Doped black phosphorus quantum dot thermal treatment syringeability bone cement as well as preparation and application thereof |
| CN106744856A (en) * | 2016-12-29 | 2017-05-31 | 深圳大学 | A kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387609B (en) * | 2014-11-18 | 2018-06-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of cellulose porous adsorbing material |
| CN106744854B (en) * | 2016-12-29 | 2019-04-26 | 深圳大学 | A kind of graphene/black phosphorus quantum dot/nitrogen containing plasma liquid composite aerogel and preparation method thereof |
| CN107163262A (en) * | 2017-05-18 | 2017-09-15 | 林向阳 | A kind of preparation method of cellulose composite aquogel |
| CN108084460A (en) * | 2017-11-15 | 2018-05-29 | 深圳大学 | A kind of cellulose/black phosphorus quantum dot composite hydrogel and preparation method thereof |
-
2017
- 2017-11-15 CN CN201711128430.1A patent/CN108084460A/en active Pending
-
2018
- 2018-08-13 WO PCT/CN2018/100243 patent/WO2019095753A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423614A (en) * | 2008-11-14 | 2009-05-06 | 武汉大学 | Luminescent fibre hydrogel and preparation method thereof |
| CN106190120A (en) * | 2016-06-30 | 2016-12-07 | 深圳先进技术研究院 | A kind of black phosphorus quantum dot and preparation method thereof |
| CN106668951A (en) * | 2016-11-23 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Doped black phosphorus quantum dot thermal treatment syringeability bone cement as well as preparation and application thereof |
| CN106744856A (en) * | 2016-12-29 | 2017-05-31 | 深圳大学 | A kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SUN ZHENGBO ET AL.: "Ultrasmall Black Phosphorus Quantum Dots: Synthesis and Use as Photothermal Agents", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
Cited By (11)
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|---|---|---|---|---|
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| CN110862559A (en) * | 2019-11-29 | 2020-03-06 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-strength cellulose/bentonite composite hydrogel |
| CN110862559B (en) * | 2019-11-29 | 2022-08-09 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-strength cellulose/bentonite composite hydrogel |
| CN111265714A (en) * | 2020-03-11 | 2020-06-12 | 四川大学 | Black phosphorus functionalized injectable hydrogel and preparation method and application thereof |
| CN112321861A (en) * | 2020-11-08 | 2021-02-05 | 天津大学 | Phosphorylated cellulose nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof |
| CN112321861B (en) * | 2020-11-08 | 2023-07-25 | 天津大学 | Cellulose phosphate nanofiber/black phosphorus quantum dot composite flame-retardant film and preparation method thereof |
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