CN102295726B - Inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel - Google Patents
Inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel Download PDFInfo
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Abstract
The invention relates to the field of the environment sensitive type high polymer material, specifically to an inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel, and a preparation method thereof. The hydrogel is characterized in that: quantum dots and rhodamine are encapsulated in a thermo sensitive hydrogel to form the inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel. According to the present invention, a fluorescence resonance energy transfer system exists in the composite hydrogel provided by the present invention, such that the hydrogel can be adopted as a controlled-release drug carrier, and the hydrogel can be provided for tracing the drug.
Description
Technical field
The present invention relates to the environment sensitive type polymeric material field, be specifically related to a kind of inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel and preparation method thereof.
Background technology
The intelligent aqueous gel capable material is the hydrophilic polymer that the class variation that environment (as temperature, pH value, light, electricity, magnetic, particular organisms signal etc.) is small to external world or stimulation have the three-dimensional net structure of significantly replying.Wherein, poly N-isopropyl acrylamide (PNIPAM) hydrogel is to study to obtain a class Thermo-sensitive material comparatively widely, Tanaka in 1984 have reported the temperature-sensing property of this hydrogel first, be characterized in existing a low critical phase temperature (LCST) in temperature transition zone, when hydrogel gel swelling lower than this temperature the time, surpass this temperature volume shrink rapidly (Tanaka T, Hirokawa Y.Volume phase transitions of ionized Nisopropylacrylamide gels.Chem Phys, 1987,81 (2): 1392-1395).
Tradition temperature-sensitive hydrogel bad mechanical property, the recoverability that dewaters again after the slow and swelling of environmental stimulus response speed is poor to external world, has greatly limited its range of application.In recent years, along with nano material is more and more applied in peculiar performances in aspect such as mechanics, optics, chemically reactives, the investigator starts compound by nano material and temperature-sensitive hydrogel, thereby has realized significantly improving the purpose of traditional hydrogel properties.The Haraguchi study group of Japan has prepared poly N-isopropyl acrylamide (PNIPAM) and lithium algae soil (nano material of laminate structure) composite aquogel, its tensile strength is about 10 times of traditional hydrogel, elongation at break, up to 1300%, is 50 times of traditional hydrogel; And toughness of material is high, the transparency also good (Haraguchi K, Takehisa T, Fan S.Macromolecules, 2002,35:10162-10171).Hern á ndez etc. has also prepared poly-hydroxyethyl acrylate-silica nanometer compound water congealing glue material by sol-gel method, storage modulus during composite aquogel expanded state that content is 30% silicon-dioxide can promote nearly 57 times (Hern á ndez J C R, Pradas M M, Ribelles J L G.J.Non-Cryst.Solids, 2008,354:1900-1908).Lee etc. adopt UV light-induced polymerization process, make polymer with excellent anti-microbial property-Ag nano particle composite hydrogel (Lee W F, Tsao K T.J.Appl.Polym.Sci.2006,100:3653-3661).
The above composite aquogel is all undertaken compound by the particle by nano-scale and warm water gel, can make a series of Nanometer composite hydrogels with excellent properties.Their mechanical property, optical property, thermomechanical property etc. have raising in various degree, and can also keep original performance, as Thermo-sensitive, pH susceptibility and biocompatibility etc.But the compound block temperature-sensitive hydrogel of inorganic fluorescence quantum also rarely has report, the common compound constructed FRET (fluorescence resonance energy transfer) system of especially inorganic fluorescence quantum and organic fluorescence probe does not also have research to relate in the hydrogel field.
Therefore, the nano material of adulterating in the composite aquogel of leading that appeared in the newspapers only can provide the raising of single performance, and the nano material of simultaneously giving two kinds of hydrogels and above high-performance have not been reported, thereby has limited it and applied more widely.At present, also there is no at present a kind ofly both temperature was had to response function fast, there is high transmission rate and high withstand voltage properties simultaneously, also there is the block hydrogel of tool fluorescent characteristics and FRET (fluorescence resonance energy transfer) system.
Summary of the invention
The object of the present invention is to provide a kind of fast temperature response that has, but the heeling-in type temperature-sensitive hydrogel of high resistance to pressure and fluorescent characteristic, temperature is had to response fast, there is fluorescent characteristic and can realize FRET (fluorescence resonance energy transfer), can become the excellent pharmaceutical carrier of capable of realizing controlled-release and traceable type.
The invention discloses inorganic fluorescent quantum dot-rhodamine composite block thermo sensitive hydrogel, is that hydrogel internal package quantum dot and rhodamine form.Have high-temperature susceptibility, lowest critical solution temperature is 35 ℃; Transmittance is more than 90%; After can bearing the pressure of 70MPa and removing pressure, recover rapidly and without distortion; Can send the fluorescence of visible waveband and have the FRET (fluorescence resonance energy transfer) system, its photoluminescence peak is: 508nm (green glow) and 579nm (ruddiness).The wherein preferred CdTe quantum dot of quantum dot or CdSe quantum dot, the preferred rhodamine B of rhodamine or rhodamine 6G.
The further preferred CdTe quantum dot of quantum dot, the further preferred rhodamine B of rhodamine.
Compound temperature-sensitive hydrogel of the present invention can be by monomer, linking agent, and initiator, accelerator, quantum dot and rhodamine are polymerized.Can adopt the low temperature polymerization method, form under the condition that quantum dot, rhodamine and monomer exist at linking agent, initiator and accelerator, preparation under the temperature of reaction of-4 ℃-4 ℃ and obtaining.The method simplicity of design, reaction medium is water, and not with an organic solvent, aftertreatment is simple, and the reaction conditions gentleness is a kind of method of the desirable compound block hydrogel of preparation.
The preparation method of compound temperature-sensitive hydrogel of the present invention comprises:
A. get quantum dot solution 0.5-1ml, rhodamine solution 0.5-1ml, by monomer N, NIPA (MPA) is dissolved in above-mentioned mixing solutions, and ultrasonic dissolution, until form clear solution;
B. add successively linking agent, initiator, accelerator N, N, N, N-Tetramethyl Ethylene Diamine (TEMED), often add a kind of reagent all to need to mix;
C. under low temperature, reaction obtains the transparent cake hydrogel in 1-2 hour;
D. after question response liquid is completed into gel, taking-up is put into deionized water and is soaked, and changes ionized water, removes unreacted monomer.General preferred immersion 6d, change deionized water every day one time, to remove unreacted monomer.
The wherein preferred N,N methylene bis acrylamide of linking agent (BIS), N, N '-eight methylene-bisacrylamide, N, N '-dodecane methylene-bis acrylic amine, N, N '-diallyl tartrate diamide or methylol acrylic amine.Further preferred N, N '-methylene-bisacrylamide.
Initiator initiator system of ammonium persulfate (APS), Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or N, N, N ', N '-Tetramethyl Ethylene Diamine.Further initiator system of ammonium persulfate.
In above-mentioned preparation method, temperature of reaction is controlled at-4 ℃～4 ℃, more preferably 4 ℃.
Wherein linking agent preferably is made into the aqueous solution of 20-50mg/ml; Accelerator preferably is made into the aqueous solution of 30-80mg/ml; Rhodamine preferably is made into the aqueous solution of 1-50 μ g/ml.
Wherein the mass ratio of quantum dot, rhodamine, monomer, linking agent, initiator, accelerator is preferably 1.2: 0.1～0.5: 100: 5: 5: 1.More preferably 1.2: 0.1: 100: 5: 5: 1.
Zhuan Yinfeng etc. have reported the temperature of reaction of utilizing 25 ℃ and have prepared the copolymerization temperature-sensitive hydrogel of NIPA (NIPA) with sodium acrylate (SA) and sodium methacrylate (SMA); Such swelling behavior when swelling contraction speed does not have obvious superiority (Zhuan Yinfeng, Wang Guowei, Zhu Zhongqi, Song Chongjian, pay state and the thermotolerance of building water in big .NIPA class copolymerization temperature-sensitive hydrogel, Zhengzhou University's journal (Edition), 2003,35:62-66).Zhou Shuhua etc. have reported a kind of poly N-isopropyl acrylamide/clay nano hydrogel, its swelling ratio is compared with the poly N-isopropyl acrylamide hydrogel, can be increased to 36 (Zhou Shuhua by 26, Liu Jian, Yang Jianguo, Wu Chengpei. the synthetic and performance of poly N-isopropyl acrylamide/clay nano hydrogel. polymer material science and engineering, 2004,20 (3): 84-87).Composite aquogel of the present invention has high transmission rate (>90%), and swelling ratio is greater than 70%, has excellent swelling behavior.Song Hongyan etc. have reported a kind of temperature sensitive PNIPA/ bentonite Composite Hydrogels, the ultimate compression strength of this hydrogel is 0.05MPa (Song Hongyan, He Suqin, Liu Wentao, Yang Mingcheng, Zhu Chengshen. the synthetic performance study that reaches of temperature sensitive PNIPA/ bentonite Composite Hydrogels radiation method. radiation research and radiation process journal .2007,25 (4): 216-220).Composite aquogel of the present invention has high withstand voltage properties, and its ultimate compression strength reaches 70MPa.
The research discovery, temperature of reaction can affect transparency and the swelling ratio of hydrogel; When differing in 10 ℃, temperature of reaction and transformation temperature be difficult to obtain the hydrogel of transparence.When temperature of reaction is higher, along with research of chaotic phenomenon can occur for the system of reacting of polyreaction, and expand to rapidly whole system from top to bottom, form milky opaque gel, i.e. inhomogeneous heterogeneous hydrogel.The chainpropagation of polymerization process is thermopositive reaction, and chain reaction speed is fast, and therefore, within the extremely short time, meeting produces a large amount of heat of polymerizations and can't distribute in time, causes local heating and reaches monomer and the phase change zone of polymers soln; Higher than the phase transition temperature (phase transition temperature of the NIPA aqueous solution is 35 ℃ of left and right) of solution, cause the gelation under a kind of phase-separated state, thereby produce inhomogeneous heterogeneous hydrogel.But then, thus when polymeric reaction temperature is too low, speed of reaction slows down and affects monomer polymerization, therefore, in order to obtain transparent this experimental selection of hydrogel polymerization temperature, is-4 ℃-4 ℃.
Research shows, quantum dot-rhodamine composite block thermo sensitive hydrogel of the present invention has good temperature-sensing property.As shown in Figure 1, by the sign of it having been carried out to transformation temperature in the variation of 500nm place transmittance of this hydrogel under differing temps, point out this plural gel rapid to temperature response, LCST is 35 ℃.The introducing of quantum dot and rhodamine does not have the LCST of remarkably influenced hydrogel, but can improve the swelling ratio of hydrogel with voltage endurance capability and low temperature the time.As shown in Figure 2, by measuring the swelling ratio of the block temperature-sensitive hydrogel of quantum dot under differing temps-rhodamine, can show that the highest swelling ratio of this composite aquogel can reach more than 70%.Due to the existence of quantum dot and rhodamine, make in gel network and formed more capillary channel on the one hand, thereby make equilibrium swelling than increasing; Part quantum dot and rhodamine have occupied the internally crosslinked networking of gel hole on the other hand, resisted the stress be subject in a part of swelling behavior process, make the single hydrogel network of this network more lax, thereby, while making swelling equilibrium, the content in conjunction with water in gel increase relatively.And, when high temperature, the swelling ratio difference of two kinds of gels is very little, this is because in high-temperature medium, in macromolecular chain or interchain produce strong hydrophobic interaction and in contraction schedule, now, the swelling ratio of gel and quantum dot and rhodamine exist relation little.
Research is discovery also, and quantum dot and the rhodamine concentration of composite water gel internal package of the present invention are higher, and space length between the two and the spectral signature of itself have met the condition of FRET (fluorescence resonance energy transfer) (FRET).As shown in Figure 3, in composite aquogel, by increasing the ratio of CdTe quantum dot, not only make the fluorescence intensity at 508nm place increase, and the also corresponding enhancing of the fluorescence intensity at 579nm place.Therefore, its result shows to have the FRET (fluorescence resonance energy transfer) system in this composite water gel.These characteristics, both given the feature of quantum dot-rhodamine compound temperature-sensitive hydrogel as the controllable released type pharmaceutical carrier, also given this hydrogel and medicine has been carried out to the function of spike simultaneously.
Preferred preparation method comprises following process:
(1) the monomer NIPA is added in the mixed aqueous solution of CdTe quantum dot and rhodamine B, at room temperature constant speed stirs, and forms the clear solution of homogeneous;
(2) add successively linking agent N, N '-methylene-bisacrylamide, initiator ammonium persulfate, accelerator N, N, N, N-Tetramethyl Ethylene Diamine (TEMED), often add a kind of reagent all to mix by magnetic agitation.
(3) under 3 ± 1 ℃ of low temperature, reaction obtains the transparent cake hydrogel in 1-2 hour.
Preparation method's of the present invention advantage is: synthesis technique is simple, obtains quantum dot-rhodamine compound temperature-sensitive hydrogel, and temperature is had to responding ability fast, and its lowest critical solution temperature is 35 ℃; This compound block hydrogel has high resistance to pressure and fluorescent characteristics simultaneously, under the exciting of light source, the fluorescence of quantum dot and rhodamine can be detected simultaneously.Because quantum dot and the rhodamine concentration of this composite water gel internal package are higher, space length between the two and the spectral signature of itself have met the condition of FRET (fluorescence resonance energy transfer) (FRET), therefore, the FRET (fluorescence resonance energy transfer) phenomenon can be detected in this composite water gel.These characteristics, both given the feature of quantum dot-rhodamine composite aquogel as the controllable released type pharmaceutical carrier, also given this hydrogel and medicine has been carried out to the function of spike simultaneously.
The accompanying drawing explanation:
The block temperature-sensitive hydrogel of quantum dot under Fig. 1 differing temps-rhodamine at the 500nm place transmittance changes.The transmittance that lowest critical solution temperature is the 500nm place occurs 50% and changes corresponding temperature.
The impact of Fig. 2 differing temps on the swelling ratio of the block temperature-sensitive hydrogel of quantum dot-rhodamine
The different quantum dot proportioning impact on the rhodamine fluorescence intensity in the block temperature-sensitive hydrogel of Fig. 3 quantum dot-rhodamine.
Embodiment
Embodiment 1
100mg monomer NIPA is added in the mixed system of the 0.5ml CdTe quantum dot aqueous solution and the 0.25ml rhodamine B aqueous solution, ultrasonic dissolution at room temperature, form the clear solution of homogeneous; Add successively linking agent N, N '-methylene-bisacrylamide 200 μ l, initiator ammonium persulfate 180 μ l, accelerator N, N, N, N-Tetramethyl Ethylene Diamine (TEMED) 20 μ l, often add a kind of reagent all to mix by magnetic agitation.Under 4 ℃ of low temperature, reaction obtains the transparent cake hydrogel in 1 hour.This product transparency is high, and transmittance is greater than 90%; There are two characteristic fluorescence peaks of 508nm and 579nm; Its swelling ratio is 60.2%; Still can return to original state after bearing the pressure of 70Mpa.
Embodiment 2
100mg monomer NIPA is added in the mixed system of the 0.625mlCdTe quantum dot aqueous solution and the 0.125ml rhodamine B aqueous solution, ultrasonic dissolution at room temperature, form the clear solution of homogeneous; Add successively linking agent N, N '-methylene-bisacrylamide 200 μ l, initiator ammonium persulfate 180 μ l, accelerator N, N, N, N-Tetramethyl Ethylene Diamine (TEMED) 10 μ l, often add a kind of reagent all to mix by magnetic agitation.Under 0 ℃ of low temperature, reaction obtains the transparent cake hydrogel in 1.5 hours.This product transparency is high, and transmittance is greater than 90%; There are 508nm and 579nm two characteristic fluorescence peaks, place; Its swelling ratio is 66.2%; Still can return to original state after bearing the pressure of 70Mpa.
Embodiment 3
100mg monomer NIPA is added in the mixed system of the 0.75ml CdTe quantum dot aqueous solution and the 0.125ml rhodamine B aqueous solution, ultrasonic dissolution at room temperature, form the clear solution of homogeneous; Add successively linking agent N, N '-methylene-bisacrylamide 200 μ l, initiator ammonium persulfate 180 μ l, accelerator N, N, N, N-Tetramethyl Ethylene Diamine (TEMED) 15 μ l, often add a kind of reagent all to mix by magnetic agitation.Under 4 ℃ of low temperature, reaction obtains the transparent cake hydrogel in 1 hour.This product transparency is high, and transmittance is greater than 90%; There are two characteristic fluorescence peaks of 508nm and 579nm; Its swelling ratio is 73.7%; Still can return to original state after bearing the pressure of 70Mpa.
Claims (7)
1. a compound temperature-sensitive hydrogel is characterized in that: by temperature-sensitive hydrogel, formed, and its internal package quantum dot and rhodamine, wherein temperature-sensitive hydrogel is the hydrogel that NIPA is monomer.
2. the compound temperature-sensitive hydrogel of claim 1, wherein quantum dot is CdTe quantum dot or CdSe quantum dot; Rhodamine is rhodamine B or rhodamine 6G.
3. the compound temperature-sensitive hydrogel of claim 1, wherein quantum dot is the CdTe quantum dot; Rhodamine is rhodamine B.
4. the preparation method of the compound temperature-sensitive hydrogel of claim 1 comprises:
A. get quantum dot solution 0.5-1ml, rhodamine solution 0.5-1ml, be dissolved in NIPA in above-mentioned mixing solutions, and ultrasonic dissolution, until form clear solution;
B. add successively linking agent, initiator, accelerator N, N, N', the N'-Tetramethyl Ethylene Diamine, often add a kind of reagent all to mix by magnetic agitation;
C. under controlling-4 ℃～4 ℃, react and within 1～2 hour, obtain the transparent cake hydrogel;
D. after question response liquid is completed into gel, taking-up is put into deionized water and is soaked, and changes ionized water, removes unreacted monomer.
5. the preparation method of claim 4, wherein linking agent is N, N '-methylene-bisacrylamide; Initiator is Potassium Persulphate.
6. the preparation method of claim 4, wherein linking agent is made into the aqueous solution of 20-50mg/ml; Accelerator is made into the aqueous solution of 30-80mg/ml; Rhodamine is made into the aqueous solution of 1-50 μ g/ml.
7. the preparation method of claim 4, wherein the mass ratio of quantum dot, rhodamine, monomer, linking agent, initiator, accelerator is 1.2:0.1～0.5:100:5:5:1.
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| CN103937504B (en) * | 2014-04-29 | 2016-03-02 | 武汉工程大学 | A kind of rhodamine-quanta point biological fluorescent probe and preparation method thereof |
| CN104804722B (en) * | 2015-05-12 | 2017-11-17 | 武汉理工大学 | A kind of temperature sensitive intelligent fluorescent nano probe and preparation method thereof |
| CN105440188B (en) * | 2015-12-15 | 2018-01-23 | 苏州大学 | A kind of novel three-dimensional gel gauge material and preparation method thereof |
| CN109627464B (en) * | 2018-05-30 | 2021-07-06 | 齐鲁工业大学 | Fluorescent probe polymer hydrogel and preparation method thereof |
| CN109809425A (en) * | 2019-03-06 | 2019-05-28 | 西南石油大学 | Based on the temperature-sensitive Self-plugging bentonite intelligently to form a film, its application and drilling fluid |
| CN109999735B (en) * | 2019-03-25 | 2021-07-30 | 天津大学 | Rare earth nucleoside white-light hydrogel and preparation method and application thereof |
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| KR100621190B1 (en) * | 2005-08-22 | 2006-09-07 | 광주과학기술원 | Quantum dots containing poly(2-vinylpyridine)-b-poly(n-hexylisocyanate) block copolymer and process for preparing them |
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| Jim Li et al..Highly PhotoluminescentCdTe/Poly(N-isopropylacrylamide)Temperature-Sensitive Gels.《Advanced Materials》.2005,第17卷(第2期),163-166. |
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