CN106187996B - A kind of composite hydrogel and its preparation method and application containing rare earth compounding of novel pH responses - Google Patents
A kind of composite hydrogel and its preparation method and application containing rare earth compounding of novel pH responses Download PDFInfo
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- CN106187996B CN106187996B CN201610534312.XA CN201610534312A CN106187996B CN 106187996 B CN106187996 B CN 106187996B CN 201610534312 A CN201610534312 A CN 201610534312A CN 106187996 B CN106187996 B CN 106187996B
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- 0 C*C1C(C(OIIC)=O)=CN(C(CC2)=CCC2F)c(cc2N3CCNCC3)c1cc2F Chemical compound C*C1C(C(OIIC)=O)=CN(C(CC2)=CCC2F)c(cc2N3CCNCC3)c1cc2F 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
- C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The present invention provides a kind of composite hydrogels and its preparation method and application containing rare earth compounding of novel pH responses.The composite hydrogel containing rare earth compounding of novel pH responses provided by the present invention is near-spherical, and grain size is 3~5mm；The composite hydrogel containing rare earth compounding of the novel pH responses includes rare earth compounding, is enclosed with the composite hydrogel of rare earth compounding.The composite hydrogel containing rare earth compounding of novel pH response provided by the present invention can improve the luminescent properties and light, thermally and chemically stability of rare earth compounding, have the features such as good biological compatibility, degradability, and has many advantages, such as that high sensitivity, time are short, reusable.
Description
Technical field
The invention belongs to luminescent material technical fields, and present invention relates particularly to a kind of coordinating containing rare earth for novel pH responses
Composite hydrogel of object and its preparation method and application.
Background technology
Since rare earth ion electron structure is unique, therefore shining for rare earth has high quantum yield, fluorescence lifetime length, transmitting
With the advantages that narrow, Stokes displacements are big.And rare-earth fluorescent can be to including zwitterion, protein, DNA, pH value, temperature, life
The specific analyte of substance markers object etc. generates the response of corresponding signal, therefore, rare earth luminescent material as optical sensor
It is widely used in chemistry and bioanalysis.
Although the luminescent properties of rare earth compounding are very excellent, it there are light, the great drawback of thermal stability difference, this
Seriously limit its actual application value and range.
Sodium alginate be universally present in brown seaweed in a kind of natural macromolecule amylose.Due to containing on its chain
There are the hydrophilic radicals such as a large amount of carboxyl and hydroxyl, makes sodium alginate that there is good hydrophily and pH responses, while its chain
On carboxyl can be with such as Ca2+、Zn2+、Al3+Deng multivalent ion combine, convenient for forming ionomer type hydrogel.Simultaneously
Sodium alginate is used for drug delivery system as pH response water gels, is also due to it and possesses good bio-compatibility, biology
The features such as degradability and nontoxicity.Therefore seaweed acid gel is usually used in biomedical research, but its mechanical stability have it is to be strengthened.
Agar has higher mechanical strength, can form the reversible hydrogel of temperature, has good thickening properties, therefore agar can be used as
Thickener, stabilizer, moisturizer and setting agent.Existing research is broken it using sodium alginate and agar as mixed carrier
Stress is probed into, the results showed that, as agar content increases, fracture strength can also respond enhancing.
Currently, not yet studies have reported that the mixed carrier of alginate and agar as rare earth compounding.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of novel pH responses containing rare earth compounding
Composite hydrogel and its preparation method and application.
In a first aspect, the present invention provides a kind of composite hydrogel containing rare earth compounding of novel pH responses, it is described
The composite hydrogel containing rare earth compounding of novel pH responses includes rare earth compounding, is enclosed with the Compound Water of rare earth compounding
Gel；
The rare earth compounding is that soluble rare-earth salt and fluorine quinolone compounds reaction are made, wherein described solvable
Property rare-earth salts and the fluorine quinolone compounds molar ratio be 1:3；
The composite hydrogel for being enclosed with rare earth compounding is agar, soluble alginate, the rare earth compounding
It is made with soluble multi-valent metal salt solution cross-linking reaction after mixing in water, wherein the agar and soluble alginate
Mass ratio be 1：1~5；The mass ratio of the rare earth compounding and soluble alginate is 1:200~1000；It is described solvable
Property multivalent metal salt to account for the mass percent of the soluble polyvalent metal saline solution be 1~5%.
Preferably, the composite hydrogel containing rare earth compounding of the novel pH response is near-spherical, grain size is 3~
5mm；
It is further preferred that the grain size of the composite hydrogel containing rare earth compounding of the novel pH response be 3.5~
4mm。
Preferably, the soluble rare-earth salt is rare earth-iron-boron, and the rare earth-iron-boron includes but not limited to EuCl3·
6H2O、TbCl3·6H2O、TmCl3·6H2O、DyCl3·6H2O、ErCl3·6H2O、SmCl3·6H2O、GdCl3·6H2In O
It is one or more of.
It is further preferred that the rare earth-iron-boron is EuCl3·6H2O or TbCl3·6H2O。
It is further preferred that the rare earth-iron-boron is that rare earth oxide is dissolved in concentrated hydrochloric acid, heating stirring boils off more
After remaining water and hydrochloric acid, cooling, crystallization is made, wherein chlorine element in the rare earth element and concentrated hydrochloric acid in the rare earth-iron-boron
Molar ratio be 1:5~10.
Preferably, the fluorine quinolone compounds include but not limited to Orbifloxacin, sarafloxacin hydrochloride, oxygen fluorine sand
One or more of star, Enrofloxacin and Ciprofloxacin.
It is further preferred that the fluorine quinolone compounds are Orbifloxacin or sarafloxacin hydrochloride.
Preferably, the soluble alginate includes but not limited to one in sodium alginate, potassium alginate, ammonium alginate
Kind is several.
It is further preferred that the soluble alginate is sodium alginate.
Preferably, the mass ratio of the soluble multivalent metal salt and soluble alginate is 0.5~3:1.
Preferably, the soluble multivalent metal salt is soluble calcium salt, and the solubility multivalent metal salt is solubility
Calcium salt, the soluble calcium salt include but not limited to one or more of calcium chloride, calcium sulfate and calcium hydroxide.
It is further preferred that the solubility multivalent metal salt is calcium chloride.
Preferably, the preparation method of the composite hydrogel for being enclosed with rare earth compounding, includes the following steps：
After agar, soluble alginate are mixed in water, the rare earth compounding is added, after stirring 15~60min
Mixed solution is obtained, then the mixed solution is instilled in soluble polyvalent metal saline solution, 15~60min of arrest reaction,
Washing, the dry composite hydrogel containing rare earth compounding that novel pH responses are made.
Second aspect, the present invention provides a kind of preparations of the composite hydrogel containing rare earth compounding of novel pH responses
Method includes the following steps：
(1) after mixing soluble rare-earth salt and fluorine quinolone compounds in water, it is molten that alkali compounds adjusting is added
The pH value of liquid be 7.0~9.0, be stirred to react 1.5~3h, then centrifuge, wash, be dried to obtain rare earth compounding, wherein it is described can
The molar ratio of dissolubility rare-earth salts and the fluorine quinolone compounds is 1:3；
(2) after mixing agar, soluble alginate in water, the rare earth compounding obtained by step (1), stirring is added
Mixed solution is obtained after 15~60min, then the mixed solution is instilled in soluble polyvalent metal saline solution, arrest reaction
15~60min, washing, the dry composite hydrogel containing rare earth compounding that novel pH responses are made, wherein the agar with
The mass ratio of soluble alginate is 1：1~5；The quality of rare earth compounding and soluble alginate obtained by step (1)
Than being 1：200~1000；The solubility multivalent metal salt accounts for the mass percent of the soluble polyvalent metal saline solution
For 1~5% (preferably 3%).
Preferably, in the step (1), the soluble rare-earth salt is rare earth-iron-boron, and the rare earth-iron-boron includes
But it is not limited to EuCl3·6H2O、TbCl3·6H2O、TmCl3·6H2O、DyCl3·6H2O、ErCl3·6H2O、SmCl3·6H2O、
GdCl3·6H2One or more of O.
It is further preferred that in the step (1), the rare earth-iron-boron is EuCl3·6H2O or TbCl3·6H2O。
It is further preferred that in the step (1), the rare earth-iron-boron is that rare earth oxide is dissolved in concentrated hydrochloric acid,
After heating stirring boils off extra water and hydrochloric acid, cooling, crystallization is made, wherein rare earth element in the rare earth-iron-boron with
The molar ratio of chlorine element is 1 in concentrated hydrochloric acid:5~10.
Preferably, in the step (1), the fluorine quinolone compounds include but not limited to Orbifloxacin, hydrochloric acid sand
One or more of Flucloxacillin, Ofloxacin, Enrofloxacin and Ciprofloxacin.
It is further preferred that in the step (1), the fluorine quinolone compounds are that Orbifloxacin or hydrochloric acid sand fluorine are husky
Star
It is understood that in the step (1), there is no special limitation to the type of the alkali compounds, it can be with
Using the alkali compounds well known to those skilled in the art for adjusting pH value.
Preferably, in the step (1), the alkali compounds is hydroxide, more preferably ammonium hydroxide.
It is further preferred that in the step (1), the mass fraction of ammonia is 25~28% in the ammonium hydroxide.
It is understood that in the step (1), in water to the soluble rare-earth salt and fluorine quinolone compounds
Mixed method does not have special limitation, and soluble rare-earth salt and fluorine quinolone compounds can be added into water.
It is understood that the present invention does not have special limitation to the method for the stirring described in the step (1), using this
The technical solution stirred known to field technology personnel.Optionally, in the step (1), the temperature of the stirring is room
The rate of temperature, the stirring is 200~400r/min, more preferably 250~350r/min.
It is understood that the present invention does not have special limitation to centrifugation, washing, dry method in the step (1),
Using centrifugation well known to those skilled in the art, washing, dry technical solution.Optionally, it in the step (1), washes
The method wash, centrifuge, dried is specially：The obtained mixtures of 1~3h of stirring are washed using absolute ethyl alcohol and centrifugation divides
After 1~3 time, rare earth compounding is made in dry 12~36h under the conditions of 50~80 DEG C.
It is understood that the present invention is to the side that mixes agar, soluble alginate in water in the step (2)
Method does not have special limitation, using the technical solution of stirring well known to those skilled in the art.Optionally, described by fine jade
The method that fat, soluble alginate mix in water, specially：The agar is added in the water boiled and dissolves and is cooled to
After temperature is not higher than 50 DEG C, the soluble alginate is added.
Preferably, it in the step (2), is added after the rare earth compounding, further includes：Power is 200~500W, temperature
Degree is is ultrasonically treated 10~15min under conditions of not higher than 50 DEG C.
It is understood that rare earth compounding is dispersed in agar and solubility sea by the supersound process in the step (2)
In alginic acid mixed salt solution, be conducive to contain the rare earth compounding in the Compound Water containing rare earth compounding in subsequent step
In gel.
It is understood that the present invention does not have special limitation to the method stirred in the step (2), using this field
The technical solution stirred known to technical staff.Optionally, in the step (2), the rate of the stirring is 200~
400r/min, more preferably 250~350r/min.
Preferably, in the step (2), the drop rate of the mixed solution is 3~5ml/min.
Preferably, in the step (2), the soluble alginate include but not limited to sodium alginate, potassium alginate,
One or more of ammonium alginate.
It is further preferred that in the step (2), the soluble alginate is sodium alginate.
Preferably, in the step (2), the mass ratio of the solubility multivalent metal salt and soluble alginate is
0.5~3:1.
Preferably, in the step (2), it is described solubility multivalent metal salt include but not limited to soluble calcium salt, it is solvable
One or more of property barium salt, aluminum soluble salt and soluble zinc salt.
Preferably, in the step (2), the solubility multivalent metal salt is soluble calcium salt, the soluble calcium salt
Including but not limited to one or more of calcium chloride, calcium sulfate and calcium hydroxide.
It is further preferred that in the step (2), the solubility multivalent metal salt is calcium chloride.
Preferably, in the step (2), the volume ratio of the mixture and the soluble multi-valent metal salt solution is 1:
3~5.
Preferably, in the step (2), the composite hydrogel containing rare earth compounding of the novel pH responses is class ball
Shape, grain size are 3~5mm；The composite hydrogel containing rare earth compounding of the novel pH responses includes rare earth compounding, package
There is the composite hydrogel of rare earth compounding.
It is further preferred that in the step (2), the composite hydrogel containing rare earth compounding of the novel pH responses
Grain size be 3.5~4mm.
Preferably, the present invention provides a kind of composite hydrogels containing rare earth compounding using described in second aspect
The composite hydrogel containing rare earth compounding obtained by preparation method.
The third aspect contains rare earth compounding the present invention also provides a kind of novel pH responses as described in relation to the first aspect
Composite hydrogel or as described in second aspect novel pH response the composite hydrogel containing rare earth compounding preparation side
Application of the method in terms of biological detection.
Preferably, the composite hydrogel containing rare earth compounding of novel pH responses as described in relation to the first aspect or such as second
Application of the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses described in aspect in pH sensings.
The beneficial effects of the present invention are：
(1) the preparation method letter of the composite hydrogel containing rare earth compounding of novel pH responses provided by the present invention
It is single, easy to operate；
(2) composite hydrogel containing rare earth compounding of novel pH responses provided by the present invention can improve rare earth cooperation
The luminescent properties and light of object, thermally and chemically stability；
(3) composite hydrogel containing rare earth compounding of novel pH responses provided by the present invention is but also with good biological
The features such as compatibility, biological degradability and nontoxicity；
(4) composite hydrogel containing rare earth compounding of novel pH response provided by the present invention in terms of pH responses again
With high sensitivity, the time is short, the advantages that being convenient for monitoring and being reusable；
(5) compared with the hydrogel (such as PVA hydrogels) of existing package rare earth compounding is without fixed shape, the present invention
The composite hydrogel containing rare earth compounding of the novel pH responses provided is spherical, and grain size is 3~5mm so that containing dilute
The application prospect of the composite hydrogel of native complex in vivo is more wide.
Description of the drawings
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of application for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the pictorial diagram for the hydrogel microsphere containing europium-Orbifloxacin complex that the embodiment of the present invention is provided；
Fig. 2 is the SEM figures for the hydrogel microsphere containing europium-Orbifloxacin complex that the embodiment of the present invention is provided；
Europium-Orbifloxacin complex (a) that Fig. 3 embodiment of the present invention is provided and the hydrogel containing europium-Orbifloxacin
The launching light spectrogram of microballoon (b)；
Fig. 4 is the hydrogel microsphere containing europium-Orbifloxacin complex that is provided of the embodiment of the present invention in different pH value
Under spectrogram；
Fig. 5 is that the hydrogel microsphere containing europium-Orbifloxacin complex that the embodiment of the present invention is provided responds pH
Invertibity；
Fig. 6 is the material object for the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that the embodiment of the present invention is provided
Figure；
Fig. 7 is the SEM for the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that the embodiment of the present invention is provided
Figure；
Fig. 8 is terbium-sarafloxacin hydrochloride complex (c) that the embodiment of the present invention is provided and husky containing terbium-hydrochloric acid sand fluorine
The launching light spectrogram of the hydrogel microsphere (d) of star；
Fig. 9 is the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that is provided of the embodiment of the present invention in difference
Spectrogram under pH value；
Figure 10 is that the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that the embodiment of the present invention is provided rings pH
The invertibity answered.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
This part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
There is the every other embodiment obtained under the premise of making creative work, shall fall within the protection scope of the present invention.
Embodiment 1
An embodiment of the present invention provides a kind of preparation method of the hydrogel microsphere containing europium-Orbifloxacin complex, packets
Include following steps：
(1) it is 1 according to the molar ratio of chlorine element in europium element in europium oxide and concentrated hydrochloric acid:8 ratio, weighs Eu2O3In burning
In cup, concentrated hydrochloric acid is added and makes it completely dissolved, thermal agitation to be added stops after boiling off extra water and hydrochloric acid, waits for its cooling, crystallization
After can obtain EuCl3·6H2O is spare；
(2) EuCl obtained by 6mmol Orbifloxacins and 2mmol steps (1) is taken3·6H2O is dissolved in 30ml deionized waters
In, and constantly dissolved under magnetic agitation under 300r/min rotating speeds；Then with weak aqua ammonia, (mass fraction of ammonia is in weak aqua ammonia
25%) solution ph is adjusted to 9 (it can be seen that having yellow mercury oxide precipitation), is centrifuged after being stirred at room temperature 2 hours, is washed with absolute ethyl alcohol
Twice, it is placed in drying in 60 DEG C of baking ovens and obtains 157mg intermediate products europium-Orbifloxacin complex for 24 hours；
(3) 20ml deionized waters are heated, 1g agar is added after it is boiled and is completely dissolved, waits for that solution is cooled to 50
DEG C when, be added 1.5g sodium alginates after, add europium-Orbifloxacin complex obtained by 2.5mg steps (2) and 200W,
It is ultrasonically treated 15min under the conditions of 50 DEG C, mixed solution is formed after magnetic agitation 0.5h under 250r/min rotating speeds, uses injection needle
The mixed solution is instilled in the calcium chloride solution of 80ml 3% with the drop rate of 4ml/min and crosslinks to form spherical shape,
It after arrest reaction 0.5h, is cleaned with deionized water and is placed in natural air drying in surface plate, obtain the water for being enclosed with europium-Orbifloxacin
Gel micro-ball.
Structure and spectrum property test：
1. the structure of europium-Orbifloxacin complex obtained by step (2) is as shown in formula I：
The pictorial diagram for the hydrogel microsphere containing europium-Orbifloxacin complex that 2. Fig. 1, which is the embodiment of the present invention, to be provided；
Fig. 2 is the SEM figures for the hydrogel microsphere containing europium-Orbifloxacin complex that the embodiment of the present invention is provided.
By Fig. 1 and Fig. 2 it is found that the hydrogel containing europium-Orbifloxacin complex obtained by the present embodiment step (3) is micro-
Ball bead spherical in shape, grain size 4mm.And under SEM observations, the compact structure of hydrogel shows its satisfactory mechanical property, can use
In practical application.
3. europium-Orbifloxacin complex is dispersed in water with the concentration of 0.1mg/ml, surveyed under the monitoring wavelength of 360nm
The launching light spectrogram of europium-Orbifloxacin complex and the hydrogel microsphere containing europium-Orbifloxacin complex is obtained, test result is as schemed
Shown in 3.
Fig. 3 is europium-Orbifloxacin complex (a) that the embodiment of the present invention is provided and the water-setting containing europium-Orbifloxacin
The launching light spectrogram of glue microballoon (b).From the figure 3, it may be seen that europium-Orbifloxacin complex and the water-setting containing europium-Orbifloxacin complex
The emission peak that glue microballoon is located at 580,591,615 and 655 corresponds to europium ion respectively5D0→7FJ(J=0,1,2,3) transition,
Wherein, strongest5D0→7F2(615nm) emission peak is in red light district, it will be appreciated also that observe, match containing europium-Orbifloxacin
The luminous intensity for closing the hydrogel microsphere of object is apparently higher than the luminous intensity of europium-Orbifloxacin complex.
In addition, europium-Orbifloxacin complex and hydrogel microsphere containing europium-Orbifloxacin complex ultraviolet lamp (light
Wavelength is 365nm) irradiation under show hunting pink fluorescence.
4. preparing 1molL-1NaOH solution and HCl solution, using PHS-3C types pH meter prepare respectively pH be 2.1 mould
The simulated intestinal fluid that quasi- gastric juice and pH are 7.4, then to move into constant volume in the volumetric flask of 500ml respectively spare；Respectively by the simulation stomach
Liquid and the simulated intestinal fluid are heated to 37 DEG C, the hydrogel microsphere ultrasound containing europium-Orbifloxacin complex obtained by step (3)
Disperse in simulate the gastric juice and the simulated intestinal fluid so that the concentration of the hydrogel microsphere containing europium-Orbifloxacin complex
For 0.1mg/ml, and using the hydrogel containing europium-Orbifloxacin complex obtained by Fluorescence Spectrometer difference determination step (3)
Fluorescence spectrum of the microballoon in the simulate the gastric juice and the simulated intestinal fluid observes the change of the emission peak luminous intensity at 615nm
Change situation.
Fig. 4 is the hydrogel microsphere containing europium-Orbifloxacin complex that is provided of the embodiment of the present invention in different pH value
Under spectrogram；Fig. 5 is that the hydrogel microsphere containing europium-Orbifloxacin complex that the embodiment of the present invention is provided responds pH
Invertibity.
As shown in Figure 4, under the excitation of the fixed wave length of 360nm, the hydrogel containing europium-Orbifloxacin complex is micro-
Fluorescent emission peak intensity of fluorescent emission peak intensity of the ball in the environment (pH=7.4) of simulated intestinal fluid than (pH=7) in water
It is slightly strong, and in the environment of simulate the gastric juice (pH=2.1), the hydrogel microsphere containing europium-Orbifloxacin complex
Apparent quenching occurs for fluorescence；This illustrates that Orbifloxacin can be protonated or be gone in the solution of different pH environment as ligand
The process of protonation, in addition, as shown in Figure 5, the hydrogel microsphere containing europium-Orbifloxacin complex from simulate the gastric juice to
The pH of simulated intestinal fluid can rapidly duplicate responses, recycling 10 times, fluorescence intensity weaken there is no apparent.
Embodiment 2
An embodiment of the present invention provides a kind of preparation method of the hydrogel microsphere containing europium-Orbifloxacin complex, packets
Include following steps：
(1) it is 1 according to the molar ratio of chlorine element in europium element in europium oxide and concentrated hydrochloric acid:8 ratio, weighs Eu2O3In burning
In cup, concentrated hydrochloric acid is added and makes it completely dissolved, thermal agitation to be added stops after boiling off extra water and hydrochloric acid, waits for its cooling, crystallization
After can obtain EuCl3·6H2O is spare；
(2) EuCl obtained by 6mmol Orbifloxacins and 2mmol steps (1) is taken3·6H2O is dissolved in 30ml deionized waters
In, and constantly dissolved under magnetic agitation under 250r/min rotating speeds；Then the weak aqua ammonia that the mass fraction of ammonia is 25% is used to adjust
Solution ph is centrifuged, use is anhydrous after being stirred 1.5 hours under room temperature 250r/min rotating speeds to 7 (it can be seen that having yellow mercury oxide precipitation)
Ethyl alcohol washes twice, and is placed in drying in 60 DEG C of baking ovens and obtains 139mg intermediate products europium-Orbifloxacin complex for 24 hours；
(3) 20ml deionized waters are heated, 0.5g agar is added after it is boiled and is completely dissolved, waits for that solution is cooled to
At 40 DEG C, be added 1.5g sodium alginates after, add europium-Orbifloxacin complex obtained by 1.5mg steps (2) and
300W, ultrasound 10min under the conditions of 40 DEG C, form mixed solution, with injection after magnetic agitation 15min under 300r/min rotating speeds
Syringe needle is by the mixed solution to crosslink to form ball in the calcium chloride solution of the drop rate instillation 60ml 1% of 3ml/min
Shape after arrest reaction 15h, is cleaned with deionized water and is placed in natural air drying in surface plate, obtain being enclosed with europium-Orbifloxacin
Hydrogel microsphere.
It is micro- to the obtained hydrogel containing europium-Orbifloxacin complex of this implementation according to the test method of embodiment 1
The grain size and photoluminescent property of ball are measured.The grain size for measuring the hydrogel microsphere containing europium-Orbifloxacin complex is
3.5mm, the hydrogel microsphere containing europium-Orbifloxacin complex are equal under ultraviolet lamp (wavelength of light is 365nm) irradiation
Show hunting pink fluorescence；And the hydrogel microsphere containing europium-Orbifloxacin complex is from simulate the gastric juice to simulation intestines
The pH of liquid can rapidly duplicate responses, recycling 10 times, fluorescence intensity weaken there is no apparent.
Embodiment 3
An embodiment of the present invention provides a kind of preparation method of the hydrogel microsphere containing europium-Orbifloxacin complex, packets
Include following steps：
(1) it is 1 according to the molar ratio of chlorine element in europium element in europium oxide and concentrated hydrochloric acid:8 ratio, weighs Eu2O3In burning
In cup, excessive concentrated hydrochloric acid is added and makes it completely dissolved, thermal agitation to be added stops after boiling off extra water and hydrochloric acid, wait for its cooling,
EuCl can be obtained after crystallization3·6H2O is spare；
(2) EuCl obtained by 6mmol Orbifloxacins and 2mmol steps (1) is taken3·6H2O is dissolved in 30ml deionized waters
In, and constantly dissolved under magnetic agitation under 350r/min rotating speeds；Then the weak aqua ammonia that the mass fraction of ammonia is 25% is used to adjust
Solution ph is centrifuged, with anhydrous second after being stirred 1 hour under room temperature 350r/min rotating speeds to 8 (it can be seen that having yellow mercury oxide precipitation)
Alcohol washes twice, and is placed in drying in 60 DEG C of baking ovens and obtains 142mg intermediate products europium-Orbifloxacin complex for 24 hours；
(3) 20ml deionized waters are heated, 0.3g agar is added after it is boiled and is completely dissolved, waits for that solution is cooled to
At 40 DEG C, be added 1.5g sodium alginates after, add europium-Orbifloxacin complex obtained by 2.5mg steps (2) and
500W, ultrasound 10min under the conditions of 50 DEG C, form mixed solution after magnetic agitation 1h under 250r/min rotating speeds, use injection needle
Head is by the mixed solution to crosslink to form ball in the calcium chloride solution of the drop rate instillation 100ml5% of 5ml/min
Shape after arrest reaction 1h, is cleaned with deionized water and is placed in natural air drying in surface plate, is obtained being enclosed with europium-Orbifloxacin and be matched
Close the hydrogel microsphere of object.
It is micro- to the obtained hydrogel containing europium-Orbifloxacin complex of this implementation according to the test method of embodiment 1
The grain size and photoluminescent property of ball are measured.The grain size for measuring the hydrogel microsphere containing europium-Orbifloxacin complex is
4mm, the hydrogel microsphere containing europium-Orbifloxacin complex are under ultraviolet lamp (wavelength of light is 365nm) irradiation
Reveal hunting pink fluorescence；And the hydrogel microsphere containing europium-Orbifloxacin complex is from simulate the gastric juice to simulated intestinal fluid
PH, can rapidly duplicate responses, recycle 10 times, fluorescence intensity weakens there is no apparent.
Embodiment 4
It the step of advantageous effect in order to further illustrate the present invention, repetition embodiment 1, will be in (1) the step of embodiment
" europium oxide " be substituted for " " terbium oxide ", 164mg terbiums-sarafloxacin hydrochloride complex is made, will be in 1 step of embodiment (2)
" Orbifloxacin " is substituted for " sarafloxacin hydrochloride ", and the hydrogel microsphere containing terbium-sarafloxacin hydrochloride is made.
According to the structure and spectrum property test method in embodiment 1, to terbium-sarafloxacin hydrochloride obtained by the present embodiment
And the structure and spectrum property of the hydrogel microsphere containing terbium-sarafloxacin hydrochloride are tested, test result is as follows：
1. the structure of europium-Orbifloxacin complex obtained by step (2) is as shown in formula II：
The reality for the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that 2. Fig. 6, which is the embodiment of the present invention, to be provided
Object figure；Fig. 7 is the SEM figures for the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that the embodiment of the present invention is provided.
By Fig. 6 and Fig. 7 it is found that the water-setting containing terbium-sarafloxacin hydrochloride complex obtained by the present embodiment step (3)
Glue microballoon bead spherical in shape, grain size 4.5mm.And under SEM observations, the compact structure of hydrogel shows that its mechanical performance is good
It is good, it can be used for practical application.
3. terbium-sarafloxacin hydrochloride complex is dispersed in water with the concentration of 0.1mg/ml, in the monitoring wavelength of 360nm
Under measure the emission spectrum of terbium-sarafloxacin hydrochloride complex and the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex
Figure, test results are shown in figure 8.
Fig. 8 be terbium-sarafloxacin hydrochloride complex (c) provided in an embodiment of the present invention and contain terbium-sarafloxacin hydrochloride
The launching light spectrogram of the hydrogel microsphere (d) of complex.As shown in Figure 8, terbium-sarafloxacin hydrochloride complex and contain terbium-salt
The emission peak that the hydrogel microsphere of sour Sarafloxacin complex is located at 489,545,584 and 622nm corresponds to terbium ion respectively5D4→7F6,5D4→7F5,5D4→7F4With5D4→7F3Transition, wherein it is strongest5D4→7F5(545nm) emission peak is in green light
Area, it will be appreciated also that observe, the luminous intensity of the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex is apparently higher than
The luminous intensity of terbium-sarafloxacin hydrochloride complex.
In addition, terbium-sarafloxacin hydrochloride complex and hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex are in purple
Bright-coloured green fluorescence is showed under outer lamp (wavelength of light is 365nm) irradiation.
4. measuring the hydrogel microsphere containing terbium-sarafloxacin hydrochloride according to the method for 1 step of embodiment 4.
Fluorescence spectrum, and observe the situation of change of the emission peak luminous intensity at 545nm；Test result is as shown in Figures 9 and 10.
Fig. 9 is the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex that is provided of the embodiment of the present invention in difference
Spectrogram under pH value；Figure 10 is the hydrogel microsphere containing terbium-sarafloxacin hydrochloride that is provided of the embodiment of the present invention to pH
The invertibity of response.
Fixed excitation wavelength contains terbium-sarafloxacin hydrochloride in 350nm in the environment (pH=7.4) of simulated intestinal fluid
The hydrogel microsphere of complex is slightly stronger than (pH=7) in water in fluorescent emission peak intensity, and in the environment (pH=of simulate the gastric juice
2.1) in, apparent quenching occurs for the fluorescence of the hydrogel microsphere containing terbium-sarafloxacin hydrochloride complex；This illustrates hydrochloric acid sand
The process of protonation or deprotonation can occur as ligand in the solution of different pH environment for Flucloxacillin, in addition, by Figure 10
It is found that we have also investigated its invertibity to pH responses, the pH from simulate the gastric juice to simulated intestinal fluid can rapidly repeat to ring
It answers, recycles 10 times, fluorescence intensity weakens there is no apparent.
Embodiment 5
It the step of advantageous effect in order to further illustrate the present invention, repetition embodiment 1, will be in 1 step of embodiment (1)
" europium oxide " is substituted for " dysprosia ", and " Orbifloxacin " in the step (2) in embodiment 1 is substituted for " Ciprofloxacin ", will
" calcium chloride " in embodiment 1 in step (3) is substituted for " calcium sulfate ", and the Compound Water containing dysprosium-Ciprofloxacin complex is made
Gel.According to the test method of embodiment 1 hydrogel microsphere containing dysprosium-Orbifloxacin complex obtained to this implementation
Grain size and photoluminescent property are measured.The grain size for measuring the hydrogel microsphere containing dysprosium-Orbifloxacin complex is
4.5mm, the hydrogel microsphere containing dysprosium-Orbifloxacin complex are equal under ultraviolet lamp (wavelength of light is 365nm) irradiation
Show bright-coloured yellow fluorescence；And the hydrogel microsphere containing dysprosium-Orbifloxacin complex is from simulate the gastric juice to simulation intestines
The pH of liquid can rapidly duplicate responses, recycling 10 times, fluorescence intensity weaken there is no apparent.
Embodiment 6
The step of advantageous effect in order to further illustrate the present invention, repetition embodiment 1, by the step (2) in embodiment 1
In " Orbifloxacin " be substituted for " Ofloxacin ", be made the composite hydrogel containing europium-Ciprofloxacin complex.
It is micro- to the obtained hydrogel containing europium-Ofloxacin complex of this implementation according to the test method of embodiment 1
The grain size and photoluminescent property of ball are measured.The grain size for measuring the hydrogel microsphere containing europium-Ofloxacin complex is
3.5mm, the hydrogel microsphere containing europium-Ofloxacin complex are equal under ultraviolet lamp (wavelength of light is 365nm) irradiation
Show hunting pink fluorescence；And the hydrogel microsphere containing europium-Ofloxacin complex is from simulate the gastric juice to simulation intestines
The pH of liquid can rapidly duplicate responses, recycling 10 times, fluorescence intensity weaken there is no apparent.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of composite hydrogel containing rare earth compounding of novel pH responses, which is characterized in that the novel pH responses
Composite hydrogel containing rare earth compounding includes rare earth compounding, is enclosed with the composite hydrogel of rare earth compounding；
The rare earth compounding is that soluble rare-earth salt and fluorine quinolone compounds reaction are made, wherein the solubility is dilute
Earth salt and the molar ratio of the fluorine quinolone compounds are 1:3；
The composite hydrogel for being enclosed with rare earth compounding is agar, soluble alginate, the rare earth compounding in water
It is made with soluble multi-valent metal salt solution cross-linking reaction after middle mixing, wherein the matter of the agar and soluble alginate
Amount is than being 1：1~5；The mass ratio of the rare earth compounding and soluble alginate is 1：200~1000；The solubility is more
The mass percent that valence metal salt accounts for the soluble multi-valent metal salt solution is 1~5%.
2. a kind of preparation method of the composite hydrogel containing rare earth compounding of novel pH responses, which is characterized in that including such as
Lower step：
(1) after mixing soluble rare-earth salt and fluorine quinolone compounds in water, alkali compounds is added and adjusts solution
PH value is 7.0~9.0, is stirred to react 1.5~3h, then centrifuge, wash, be dried to obtain rare earth compounding, wherein the solubility
The molar ratio of rare-earth salts and the fluorine quinolone compounds is 1:3；
(2) after agar, soluble alginate being mixed in water, the rare earth compounding obtained by addition step (1), stirring 15~
Mixed solution is obtained after 60min, then the mixed solution is instilled in soluble multi-valent metal salt solution, arrest reaction 15~
60min, washing, the dry composite hydrogel containing rare earth compounding that novel pH responses are made, wherein the agar with it is solvable
Property alginate mass ratio be 1：1~5；The mass ratio of rare earth compounding and soluble alginate obtained by step (1) is
1：200~1000；The mass percent that the solubility multivalent metal salt accounts for the soluble multi-valent metal salt solution is 1~
5%.
3. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is that the soluble rare-earth salt is rare earth-iron-boron, and the rare earth-iron-boron includes EuCl3·6H2O、TbCl3·6H2O、
TmCl3·6H2O、DyCl3·6H2O、ErCl3·6H2O、SmCl3·6H2O、GdCl3·6H2One or more of O.
4. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is that the fluorine quinolone compounds include Orbifloxacin, sarafloxacin hydrochloride, Ofloxacin, Enrofloxacin and ring third
One or more of Sha Xing.
5. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is that the soluble alginate includes one or more of sodium alginate, potassium alginate and ammonium alginate.
6. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is that the solubility multivalent metal salt is soluble calcium salt.
7. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is, in the step (2), the mass ratio of the solubility multivalent metal salt and soluble alginate is 0.5~3:1.
8. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is, in the step (2), the volume ratio of the mixed solution and the soluble multi-valent metal salt solution is 1:3~5.
9. the preparation method of the composite hydrogel containing rare earth compounding of novel pH responses as claimed in claim 2, special
Sign is that the composite hydrogel containing rare earth compounding of the novel pH responses is near-spherical, and grain size is 3~5mm；It is described new
The composite hydrogel containing rare earth compounding of type pH responses includes rare earth compounding, is enclosed with the compound water congealing of rare earth compounding
Glue.
10. a kind of composite hydrogel containing rare earth compounding of novel pH responses as described in claim 1 is in biological detection
The application of aspect.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1165037A (en) * | 1997-06-04 | 1997-11-19 | 天津大学 | PH value response medicine controlled release carrier |
| CN1594385A (en) * | 2004-06-18 | 2005-03-16 | 武汉大学 | Biodegradable hydrogel and method for preparing same |
| CN102171234A (en) * | 2008-08-05 | 2011-08-31 | 康奈尔大学 | Photo-crosslinked nucleic acid hydrogels |
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| CN1165037A (en) * | 1997-06-04 | 1997-11-19 | 天津大学 | PH value response medicine controlled release carrier |
| CN1594385A (en) * | 2004-06-18 | 2005-03-16 | 武汉大学 | Biodegradable hydrogel and method for preparing same |
| CN102171234A (en) * | 2008-08-05 | 2011-08-31 | 康奈尔大学 | Photo-crosslinked nucleic acid hydrogels |
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