CN107837396A - Collect the preparation method of the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy - Google Patents
Collect the preparation method of the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy Download PDFInfo
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- CN107837396A CN107837396A CN201710840893.4A CN201710840893A CN107837396A CN 107837396 A CN107837396 A CN 107837396A CN 201710840893 A CN201710840893 A CN 201710840893A CN 107837396 A CN107837396 A CN 107837396A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
- A61K31/505—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim
- A61K31/519—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim ortho- or peri-condensed with heterocyclic rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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Abstract
The present invention relates to a kind of preparation method for collecting the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy, belong to pharmaceutical carrier field.The present invention has synthesized the ferroso-ferric oxide of MTX modifications by thermal decomposition method, is acted on further through electrostatic attraction by MTX Fe3O4Successfully it is assembled into AuNPs on MTX/LDHs, obtains final product Fe3O4@MTX/LDH‑Au.The product with magnetic targeted function, with thermotherapy and chemotherapy function, realize the multifunction of pharmaceutical carrier.
Description
Technical field
The present invention relates to a kind of preparation method for collecting the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy, belong to
Pharmaceutical carrier field.
Background technology
Magnetic medicine carrier is a development prospect than broader field, it is prepared, the exploration of performance and application
As the focus of research.In preparation, magnetic Nano material is generally the microballoon of core-shell type, has had many scholars to nucleocapsid
Formula magnetic Nano material is explored.The MgFe prepared such as Duan Xue et al.2O4@IBU (brufen)/LDH magnetic composites,
Fe3O4@DFUR (FUDR)/LDH compounds and Fe3O4@SiO2@LDH microballoons；Professor Hou Wanguo etc. has synthesized Fe3O4@
LDH compounds；Shi Jianlin researcher etc. has synthesized Fe3O4@SiO2@LDH core shell structures etc..Work of this structure in external magnetic field
Under, drug delivery to target site can be improved targeting by drug-loading system.
Research to pharmaceutical carrier at present has tended to diversification, multifunction cooperative cooperating.
The content of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is：A kind of collection magnetic targeted, thermotherapy chemotherapy are provided
Integration multi-functional drug carriers preparation method, the product with magnetic targeted function, have thermotherapy and chemotherapy function, reality
The multifunction of pharmaceutical carrier is showed.
The present invention has synthesized the ferroso-ferric oxide of MTX modifications by thermal decomposition method, is acted on further through electrostatic attraction by MTX-
Fe3O4Successfully it is assembled into AuNPs on MTX/LDHs, obtains final product Fe3O4@MTX/LDH-Au。
The technical solution adopted for the present invention to solve the technical problems is：A kind of collection magnetic targeted, thermotherapy chemotherapy one are provided
The preparation method of the multi-functional drug carriers of change, comprises the following steps：
(1) using thermal decomposition method synthesis Fe3O4-MTX：
By FeCl3.6H2O is dissolved in ethylene glycol, then adds NaAc, polyethylene glycol and MTX in above-mentioned solution, stirring
Afterwards, it is transferred in autoclave, is put it into after the completion of reaction in baking oven, carries out hydro-thermal process, that is, prepared Fe3O4-
MTX nano-complexes；
(2)Fe3O4The synthesis of@MTX/LDH nano materials：
The configuration of solution A：The Fe that will newly synthesize3O4- MTX nano-complexes are added in alcohol solution, and MTX is dissolved in
NH3·H2In O, and transfer them in above-mentioned alcohol solution, this mixed solution is labeled as solution A；
Mixing salt solution B configuration：By Mg (NO3)3·6H2O and Al (NO3)3·9H2O is equally dissolved in 50mL alcohol solutions
In be made into mixing salt solution B,
Solution A is transferred in three-neck flask and is continually fed into nitrogen, then mixing salt solution B is added drop-wise in solution A,
The pH value that mixed solution is adjusted during dropwise addition is 9.5, and temperature is maintained at 60 DEG C, and magnetic agitation is simultaneously constantly passed through N2, after 1h
Stop reaction, that is, obtain product Fe3O4@MTX/LDH；
(3) synthesis of the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy is collected：
AuNPs is synthesized using seed mediated growth method, sodium citrate solution is added in round-bottomed flask, is heated to boiling in oil bath
Rise, HAuCl is then added dropwise4, solution is changed into claret from yellow, until color no longer changes, forms gold kind；Gold is planted
90 DEG C are cooled to, adds sodium citrate solution and HAuCl4, after stirring reaction, that is, obtain the golden nanometer particle that particle diameter is 30nm；
After taking the AuNPs centrifuge washings newly synthesized, it is re-dispersed into distilled water, adds it to Fe3O4@MTX/LDH receive
In rice compound, stir at room temperature, that is, obtain final product Fe3O4@MTX/LDH-Au。
Described use thermal decomposition method synthesis Fe3O4-MTX：
Weigh 1.35g FeCl3.6H2O is dissolved in 40mL ethylene glycol, then weighs the poly- second two of 3.6g NaAc, 1.0g respectively
Alcohol and 30mg MTX are added in above-mentioned solution, after stirring 30min at room temperature, are transferred to 50mL autoclaves (pressure 15-30
MPa reacted in), reaction is put it into baking oven after terminating, and 24h hydro-thermal process is carried out at 180 DEG C, that is, has prepared Fe3O4-
MTX nano-complexes.
Described Fe3O4The synthesis of@MTX/LDH nano materials：
The configuration of solution A：Accurately weigh the Fe that 50mg is newly synthesized3O4- MTX nano-complexes are added to 50mL alcohol solutions
In (ethanol, water volume ratio 1:3) 0.0341g MTX, are dissolved in 8mL 10%NH3·H2O, and transfer them to above-mentioned solution
In, this mixed solution is labeled as solution A；
Mixing salt solution B configuration：Weigh 0.07692g Mg (NO3)3·6H2O and 0.05627g Al (NO3)3·9H2O,
It is equally dissolved in 50mL alcohol solutions (ethanol, water volume ratio 1:3) mixing salt solution B is made into,
Solution A is transferred in three-neck flask and is continually fed into nitrogen, to protect the ferroso-ferric oxide in solution, then will
Mixing salt solution B is added drop-wise in solution A, adjusts the pH value of mixed solution during dropwise addition with the ammoniacal liquor that mass fraction is 10%
For 9.5, temperature is maintained at 60 DEG C, and magnetic agitation is simultaneously constantly passed through N2, stop reaction after 1h, that is, obtain product Fe3O4@MTX/
LDH。
The synthesis of described collection magnetic targeted, the multi-functional drug carriers of thermotherapy chemotherapy integration：
Au NPs are synthesized using seed mediated growth method, 150mL 0.0022mol/L sodium citrate solutions are added into round-bottomed flask
In, it is heated to seething with excitement in 137 DEG C of oil bath, 1mL 0.025mol/L HAuCl is then added dropwise4, solution becomes by yellow
For claret, until color no longer changes, formation gold is planted；
Gold kind is cooled to 90 DEG C, is rapidly added 3mL 0.06mol/L sodium citrate solutions and 1mL 0.025mol/L
HAuCl4, after magnetic agitation reacts 1h, that is, obtain the golden nanometer particle that particle diameter is 30nm；
After taking the Au NPs centrifuge washings that 20mL is newly synthesized, it is re-dispersed into 20mL distilled water, adds it to 10mL
10 mg/mL Fe3O4In@MTX/LDH nano-complexes, 5h is stirred at room temperature, that is, obtains final product Fe3O4@MTX/LDH-
Au。
The volume ratio of alcohol and water is 1 in described alcohol solution：3 (alcohol of alcohol water here is to say ethanol).
The beneficial effects of the invention are as follows：
1st, the present invention has synthesized the ferroso-ferric oxide of MTX modifications by thermal decomposition method, and being acted on further through electrostatic attraction will
MTX-Fe3O4Successfully it is assembled into Au NPs on MTX/LDHs, obtains final product Fe3O4@MTX/LDH-Au.The product has
Magnetic targeted function, there is thermotherapy and chemotherapy function, realize the multifunction of pharmaceutical carrier；
2nd, the worth Fe of the present invention3O4@MTX/LDH-Au compounds are broadly divided into two stages in PBS release, and preceding 100
Min rates of release are than very fast, and 100-500min rate of release is slower, and this is similar to MTX/LDH Drug-Release Behavior.I
It also hold that the first stage mainly adsorb in Fe3O4The release of the medicine on@MTX/LDH-Au surfaces, and the medicine of second stage
Thing release is mainly as caused by the ion exchange of interlayer drug molecule and phosphate radical anion.To sum up illustrate, Fe3O4@MTX/
LDH-Au compounds have preferable sustained release performance.
Brief description of the drawings
Fig. 1 is Fe3O4-MTX、Fe3O4@MTX/LDH and Fe3O4@MTX/LDH-Au TEM figures；
Fig. 2 is sample F e3O4-MTX、Fe3O4@MTX/LDH、Fe3O4@MTX/LDH-Au and Au-MTX XRD figures；
It is sample MTX, Fe that Fig. 3, which is,3O4-MTX、Fe3O4@MTX/LDH and Fe3O4@MTX/LDH-Au FTIR figures；
Fig. 4 is Fe3O4The elution profiles figure of@MTX/LDH-Au nano-complexes；
(A, B) sample is Fe in wherein Fig. 13O4- MTX TEM figures；(C, D) sample is Fe3O4@MTX/LDH TEM figures；
(E, F) sample is Fe3O4@MTX/LDH-Au TEM figures.
Embodiment
Embodiments of the invention are described further below in conjunction with the accompanying drawings：
Embodiment 1
As shown in figures 1-4, the present invention is to collect the preparation side of the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy
Method, comprise the following steps：
(1) using thermal decomposition method synthesis Fe3O4-MTX；
(2)Fe3O4The synthesis of@MTX/LDH nano materials；
(3) synthesis of the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy is collected.
Described use thermal decomposition method synthesis Fe3O4-MTX：
Weigh 1.35g FeCl3.6H2O is dissolved in 40mL ethylene glycol, then weighs the poly- second two of 3.6g NaAc, 1.0g respectively
Alcohol and 30mg MTX are added in above-mentioned solution, after stirring 30min at room temperature, are transferred to 50mL autoclaves (15-30MPa
Under pressure) in react, reaction terminate after put it into baking oven, at 180 DEG C carry out 24h hydro-thermal process, that is, prepare
Fe3O4- MTX nano-complexes.
Described Fe3O4The synthesis of@MTX/LDH nano materials：
The configuration of solution A：Accurately weigh the Fe that 50mg is newly synthesized3O4- MTX nano-complexes are added to 50mL alcohol solutions
In (ethanol/water volume ratio be 1:3) 0.0341g MTX, are dissolved in 8mL 10%NH3·H2O, and transfer them to above-mentioned solution
In, this mixed solution is labeled as solution A；
Mixing salt solution B configuration：Weigh 0.07692g Mg (NO3)3·6H2O and 0.05627g Al (NO3)3·9H2O,
It is equally dissolved in 50mL alcohol solutions, and (ethanol/water volume ratio is 1:3) mixing salt solution B is made into,
Solution A is transferred in three-neck flask and is continually fed into nitrogen, to protect the ferroso-ferric oxide in solution, then will
Mixing salt solution B is added drop-wise in solution A, adjusts the pH value of mixed solution during dropwise addition with the ammoniacal liquor that mass fraction is 10%
For 9.5, temperature is maintained at 60 DEG C, and magnetic agitation is simultaneously constantly passed through N2, stop reaction after 1h, that is, obtain product Fe3O4@MTX/
LDH。
The synthesis of described collection magnetic targeted, the multi-functional drug carriers of thermotherapy chemotherapy integration：
Au NPs are synthesized using seed mediated growth method, 150mL 0.0022mol/L sodium citrate solutions are added into round-bottomed flask
In, it is heated to seething with excitement in 137 DEG C of oil bath, 1mL 0.025mol/L HAuCl is then added dropwise4, solution becomes by yellow
For claret, until color no longer changes, formation gold is planted；
Gold kind is cooled to 90 DEG C, is rapidly added 3mL 0.06mol/L sodium citrate solutions and 1mL 0.025mol/L
HAuCl4, after magnetic agitation reacts 1h, that is, obtain the golden nanometer particle that particle diameter is 30nm；
After taking the Au NPs centrifuge washings that 20mL is newly synthesized, it is re-dispersed into 20mL distilled water, adds it to 10mL
10 mg/mL Fe3O4In@MTX/LDH nano-complexes, 5h is stirred at room temperature, that is, obtains final product Fe3O4@MTX/LDH-
Au。
The volume ratio of alcohol and water is 1: 3 (alcohol of alcohol water here is to say ethanol) in described alcohol solution.
From figure 1 it appears that Fe3O4- MTX is distributed than more uniform, uniform particle diameter.Measure Fe3O4- MTX Zeta electricity
Position is -40.5mV, has stronger stability, passes through electrostatic interaction, by magnalium salting liquid, MTX solution and Fe3O4Mixing,
In Fe3O4Original position is grown, and generates the Fe with core shell structure3O4@MTX/LDH nano-complexes (Fig. 1 C-D), are scheming
In see that obvious LDH shells are wrapped in Fe3O4Surface, it was demonstrated that Fe3O4The presence of@MTX/LDH nanocomposite structures.
By Fe3O4The Au NPs of@MTX/LDH and certain volume are mixed, and obtain Fe3O4@MTX/LDH-Au nano-complexes (figure
1E-F), Au NPs have successfully been adsorbed onto Fe by electrostatic attraction3O4@MTX/LDH surfaces.
Sample F e3O4-MTX、Fe3O4@MTX/LDH、Fe3O4@MTX/LDH-Au and Au-MTX XRD are shown in Fig. 2, sample
Fe3O4There is stronger characteristic peak at 30.1 °, 35.5 °, 43.1 °, 53.4 °, 57.0 ° and 62.6 ° in-MTX, and this corresponds to
Fe3O4The diffraction maximum of (220), (311), (400), (422), (511) and (440) crystal face of anti-cubic spinel structure.
Fe3O4In@MTX/LDH, except Fe3O4Outside-MTX characteristic peak, LDH diffraction maximum also be present, but intensity is not high.For Au-
It is that the strong peak occurred at 38 °, 44.6 °, 64.8 ° and 77.8 ° corresponds to Au NPs (1 1 1) in 2 θ for MTX NPs, (2
0 0), the characteristic diffraction peak of (2 2 0) and (3 1 1) crystal face.And in Fe3O4In@MTX/LDH-Au samples, Fe3O4- MTX, Au
NPs and LDH characteristic diffraction peak is present.The small figure part in the upper right corner is sample F e in XRD3O4@MTX/LDH-Au are in 2 θ
For 2-20 ° of XRD, in this figure it is apparent that the presence of LDH (0 0 3) and (0 0 6) diffraction maximum, and with
NO3- LDHs (2 θ angles corresponding to 003 characteristic diffraction peaks be 10.92 °) is compared, and (the 00 3) diffraction maximum of sample is to low angle side
To movement, show that medicine MTX is successfully inserted into LDHs interlayers.To sum up illustrate, sample F e3O4@MTX/LDH-Au synthesize into
Work(.
Fig. 3 is sample MTX, Fe3O4-MTX、Fe3O4@MTX/LDH and Fe3O4@MTX/LDH-Au FTIR figures.Sample
Fe3O4-MTX、Fe3O4@MTX/LDH and Fe3O4@MTX/LDH-Au are in 575cm-1There is Fe-O characteristic absorption peak, explanation in place
Fe3O4It is present in above-mentioned substance.Contrast each sample can find that four kinds of samples are 1614cm in wave number-1And 1100cm-1Position there is characteristic absorption peak, the two absworption peaks correspond to COO in MTX respectively-Antisymmetric vibration peak and MTX aromatic rings
The stretching vibration peak of middle primary amine and tertiary amine C-N keys, illustrates that MTX is successfully carried on Fe3O4-MTX、Fe3O4@MTX/LDH and
Fe3O4@MTX/LDH-Au nanoparticle surfaces.
Fe3O4The drugloading rate of@MTX/LDH-Au nano-complexes is 38.2%, in 37 DEG C of pH=7.4 PBS cushioning liquid
In probe into Fe3O4@MTX/LDH-Au sustained release performance (Fig. 4), as can be seen from the figure compound have obviously be sustained
Effect, elution profiles are steady, and the phenomenon of burst release of medicine does not occur.Fe3O4Release of the@MTX/LDH-Au compounds in PBS
It is broadly divided into two stages, preceding 100min rates of release are than very fast, and 100-500min rate of release is slower, this and MTX/LDH
Drug-Release Behavior it is similar.We are it also hold that the first stage is mainly to adsorb in Fe3O4The medicine on@MTX/LDH-Au surfaces
Release, and the insoluble drug release of second stage mainly caused by the ion exchange of interlayer drug molecule and phosphate radical anion
's[106].To sum up illustrate, Fe3O4@MTX/LDH-Au compounds have preferable sustained release performance.
Claims (5)
1. it is a kind of collect magnetic targeted, thermotherapy chemotherapy integration multi-functional drug carriers preparation method, it is characterised in that including with
Lower step：
(1) using thermal decomposition method synthesis Fe3O4-MTX：
By FeCl3·6H2O is dissolved in ethylene glycol, then adds NaAc, polyethylene glycol and MTX in above-mentioned solution, after stirring, is turned
Move in autoclave, put it into after the completion of reaction in baking oven, carry out hydro-thermal process, that is, prepared Fe3O4- MTX nanometers
Compound；
(2)Fe3O4The synthesis of@MTX/LDH nano materials：
The configuration of solution A：The Fe that will newly synthesize3O4- MTX nano-complexes are added in alcohol solution, and MTX is dissolved in into NH3·H2O
In, and transfer them in above-mentioned alcohol solution, this mixed solution is labeled as solution A；
Mixing salt solution B configuration：By Mg (NO3)3·6H2O and Al (NO3)3·9H2O, which is equally dissolved in 50mL alcohol solutions, to be matched somebody with somebody
Into mixing salt solution B,
Solution A is transferred in three-neck flask and is continually fed into nitrogen, then mixing salt solution B is added drop-wise in solution A, is added dropwise
During adjust mixed solution pH value be 9.5, temperature is maintained at 60 DEG C, and magnetic agitation is simultaneously constantly passed through N2, stop after 1h
Reaction, that is, obtain product Fe3O4@MTX/LDH；
(3) synthesis of the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy is collected：
AuNPs is synthesized using seed mediated growth method, sodium citrate solution is added in round-bottomed flask, is heated to seething with excitement in oil bath,
Then HAuCl is added dropwise4, solution is changed into claret from yellow, until color no longer changes, forms gold kind；Gold kind is cooled
To 90 DEG C, sodium citrate solution and HAuCl are added4, after stirring reaction, that is, obtain the golden nanometer particle that particle diameter is 30nm；
After taking the AuNPs centrifuge washings newly synthesized, it is re-dispersed into distilled water, adds it to Fe3O4@MTX/LDH nanometers are answered
In compound, stir at room temperature, that is, obtain final product Fe3O4@MTX/LDH-Au。
2. the preparation method of the integrated multi-functional drug carriers of collection magnetic targeted according to claim 1, thermotherapy chemotherapy, its
It is characterised by described use thermal decomposition method synthesis Fe3O4-MTX：
Weigh 1.35g FeCl3·6H2O is dissolved in 40mL ethylene glycol, then weigh respectively 3.6g NaAc, 1.0g polyethylene glycol and
30mg MTX are added in above-mentioned solution, after stirring 30min at room temperature, are transferred in 50mL autoclaves and are reacted, and keep pressure
Under 15-30MPa, reaction is put it into baking oven after terminating, and 24h hydro-thermal process is carried out at 180 DEG C, that is, has prepared Fe3O4-
MTX nano-complexes.
3. the preparation method of the integrated multi-functional drug carriers of collection magnetic targeted according to claim 1, thermotherapy chemotherapy, its
It is characterised by described Fe3O4The synthesis of@MTX/LDH nano materials：
The configuration of solution A：Accurately weigh the Fe that 50mg is newly synthesized3O4- MTX nano-complexes are added to its in 50mL alcohol solutions
Middle ethanol, water volume ratio 1:3,0.0341g MTX are dissolved in 8mL 10%NH3·H2O, and transfer them in above-mentioned solution,
This mixed solution is labeled as solution A；
Mixing salt solution B configuration：Weigh 0.07692g Mg (NO3)3·6H2O and 0.05627g Al (NO3)3·9H2O, by it
Equally it is dissolved in 50mL alcohol solutions and is made into mixing salt solution B, ethanol, water volume ratio 1:3；
Solution A is transferred in three-neck flask and is continually fed into nitrogen, then will mixing to protect the ferroso-ferric oxide in solution
Salting liquid B is added drop-wise in solution A, and the pH value of the ammoniacal liquor for being 10% with mass fraction during dropwise addition regulation mixed solution is 9.5,
Temperature is maintained at 60 DEG C, and magnetic agitation is simultaneously constantly passed through N2, stop reaction after 1h, that is, obtain product Fe3O4@MTX/LDH。
4. the preparation method of the integrated multi-functional drug carriers of collection magnetic targeted according to claim 1, thermotherapy chemotherapy, its
It is characterised by the described synthesis for collecting the integrated multi-functional drug carriers of magnetic targeted, thermotherapy chemotherapy：
Au NPs are synthesized using seed mediated growth method, 150mL 0.0022mol/L sodium citrate solutions are added in round-bottomed flask,
It is heated to seething with excitement in 137 DEG C of oil bath, 1mL 0.025mol/L HAuCl is then added dropwise4, it is red that solution from yellow is changed into wine
Color, until color no longer changes, formation gold is planted；
Gold kind is cooled to 90 DEG C, is rapidly added 3mL 0.06mol/L sodium citrate solutions and 1mL 0.025mol/L HAuCl4,
After magnetic agitation reaction 1h, that is, obtain the golden nanometer particle that particle diameter is 30nm；
After taking the Au NPs centrifuge washings that 20mL is newly synthesized, it is re-dispersed into 20mL distilled water, adds it to 10mL
10mg/mL Fe3O4In@MTX/LDH nano-complexes, 5h is stirred at room temperature, that is, obtains final product Fe3O4@MTX/LDH-Au。
5. the preparation method of the integrated multi-functional drug carriers of collection magnetic targeted according to claim 3, thermotherapy chemotherapy, its
The volume ratio of alcohol and water is 1 in alcohol solution described in being characterised by：3, the wherein alcohol of alcohol water here is ethanol.
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| CN108672715A (en) * | 2018-04-25 | 2018-10-19 | 安徽师范大学 | Functional modification gold nanoparticle and preparation method thereof, the detection method of metal mercury ions and its application |
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| CN106552269A (en) * | 2015-09-23 | 2017-04-05 | 南京理工大学 | A kind of pH responsive types Fe3O4The Nano medication particle of@LDH load methotrexate (MTX)s, preparation method and applications |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108672715A (en) * | 2018-04-25 | 2018-10-19 | 安徽师范大学 | Functional modification gold nanoparticle and preparation method thereof, the detection method of metal mercury ions and its application |
| CN110013559A (en) * | 2019-05-14 | 2019-07-16 | 东华大学 | A kind of extra small ferrum nano material of double-metal hydroxide-of HA targeting and its preparation and application |
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