CN108079296A - A kind of dynamic ph responds preparation method of the chain based on borate type metallo-organic complex - Google Patents
A kind of dynamic ph responds preparation method of the chain based on borate type metallo-organic complex Download PDFInfo
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Abstract
The invention belongs to biological medicine functional material preparing technical field, a kind of dynamic ph responds preparation method of the chain based on borate type metallo-organic complex.Therefore, this work introduces boric acid ylidene ligands using metallo-organic complex, upper anticancer drugs, doxorubicin (DOX) is then carried by the porous structure of metallo-organic complex, then be used for achieving the purpose that delay to discharge as dynamic response chain in the biological chain (PEG NHS PDA) for connecting hydrophilic and prevents anticancer drug from arbitrarily discharging.The sialic acid of cancer cell surfaces is identified finally by metallo-organic complex, and inhibits the growth of cancer cell by heat-therapeutic action.
Description
Technical field
The invention belongs to biological medicine functional material preparing technical field, it is related to that the present invention relates to a kind of dynamic phs to respond chain base
In the preparation method of borate type metallo-organic complex.
Background technology
As the understanding to cellular biology of tumor and science of heredity constantly understands, new therapy and means are also constantly gushed
Existing, the Therapy study of cancer has been achieved for sizable progress, and the thermotherapy of wherein tumour becomes a new hot spot.Thermotherapy
Advantage be embodied in Small side effects, with obvious effects, the advantages such as treatment cycle is short.The initial idea for the treatment of of cancer depends on defeated
Send antineoplastic chemotherapy medicine.However, drug in transmission process would generally release anti-cancer medicine so as to destroying normal cell and group
It knits, brings unnecessary drug side-effect.Therefore in order to improve the utilization ratio of pharmaceutical carrier, Mobyneb pharmaceutical carrier is developed
It is very necessary.
At present, process is the study found that sialic acid (Sialic acid) is present in a kind of substance of cancer cell surfaces, usually
Cell surface sialic acid residue number with the states of all kinds of cancers have apparent association.For this purpose, researcher by
The ligand that can be combined with cancer cell tissue with specific receptor is modified on pharmaceutical carrier, so as to fulfill carrier and specific receptor
It is affine.So as to reach by targeted drug to inhibit even to kill tumour, life quality is improved, mitigates drug accumulation band
The side effect come.Since sialic acid includes dihydroxy based structures of taking advantage of a situation, intend realizing target cancer cell using boron affinity interaction power.Boron
Affinity interaction is that boric acid ylidene ligands can generate five-membered ring structure in neutral or basic conditions with dihydroxy based structures, together
When in acid condition five yuan of ester ring structures dissociate.Metallo-organic complex causes the highest attention of scientific research recently, it
With larger specific surface area and chemical stability and excellent fuel factor.It is by metal ion and organic ligand with reference to and
Into metal ion is as central point, and organic ligand is as frame.Metallo-organic complex is largely used to light and is urged at present
Change, environmental contaminants separation, the fields such as bio-separation, but it is seldom in the report for carrying prescription face.
The content of the invention
Now to problem existing in the prior art, the present invention introduces boric acid ylidene ligands using metallo-organic complex, then leads to
The porous structure for crossing metallo-organic complex carries upper anticancer drugs, doxorubicin (DOX), then connects polyethylene glycol-dopamine again
Biological chain (PEG-NHS-PDA) is used for reaching the mesh for delaying to discharge and preventing anticancer drug from arbitrarily discharging as dynamic response chain
's.Finally by the sialic acid of metallo-organic complex identification cancer cell surfaces, and cancer cell is inhibited by heat-therapeutic action
Growth.
The present invention prepares magnetic function type boronate metal organic frame long-term sustained release drug by dual-target effect and carries
Body.First, poly-dopamine nano particle is synthesized, Dopamine hydrochloride is added in the mixed solution of second alcohol and water, and progressively dripped
Ammonification aqueous solution makes mixed solution become dark brown from yellow, then continuously stirs and dopamine polymer beads generals are prepared
The dopamine polymer beads being prepared are as carrier, then by 3,5- dicarboxyphenyis boric acid (BBDC) and 1,3,5- equal three
Benzoic acid (BTC) is as organic ligand N,N-dimethylformamide (DMF) and absolute ethyl alcohol as solvent and configuration metal ions Zn2+Make
For tie point dopamine nano grain surface length on polymer.Then upper anticancer drugs, doxorubicin is carried, is steeped in alkaline conditions
Upper PEG-NHS-PDA solution.Finally in 37 DEG C of vacuum drying.Finally, final material functional form boronate metallo-organic complex
Pharmaceutical carrier (PDA@CP-DOX-PEG) is used to identify and kill the research of cancer cell.
The technical solution adopted by the present invention is：
Dynamic ph responds preparation method of the chain based on borate type metallo-organic complex, includes the following steps：
(1) ethyl alcohol and distilled water are mixed first, then adds Dopamine hydrochloride, and 20- is dispersed with stirring with magneton
40min；Obtained solution is slowly added to ammonia spirit (28%-30%) thereto under the constant agitation of 200-400rpm, molten
Liquid become dark brown from yellow immediately and continuously stir 12-48 it is small when, and be cleaned multiple times with distilled water, and in 50-70 DEG C of condition
It is lower drying 12-48 it is small when, so as to which poly-dopamine nano particle (PDA) be prepared；
(2) by PDA obtained by step (1), zinc nitrate hexahydrate, absolute ethyl alcohol, n,N-Dimethylformamide (DMF) addition
To among the reaction ax of polytetrafluoroethylene (PTFE), 3,5- dicarboxyphenyi boric acid BBDC and 1,3,5- Trimesic acid BTC are then added in,
And the hydro-thermal polymerisation in air dry oven, it is then cooled to room temperature, is cleaned repeatedly with distilled water, finally in vacuum 50-70
It is dried at DEG C, prepared-PDA@CP (P-PDA@CP) is prepared；
(3) according to step (2) step, by P-PDA@CP and zinc nitrate hexahydrate, absolute ethyl alcohol, DMF, BBDC, BTC
Hydro-thermal polymerisation is carried out again, is cleaned, drying；The hydro-thermal polymerisation is repeated 3 times；Obtain PDA@CP；
(4) by the PDA CP that step (3) obtains be added to doxorubicin hydrochloride (DOX) aqueous solution stand 12-48 it is small when, then
The PDA@CP-DOX being prepared are cleaned multiple times with distilled water.Then PDA@CP-DOX are added to the life of polyethylene glycol-dopamine
(20mM, pH=8.5) and mechanical agitation 12-48h in the PBS buffer solutions of object chain (PEG-NHS-PDA), then distillation washing 3
Time.The PDA CP-DOX-PEG finally obtained dried at 30-50 DEG C of vacuum 12-48 it is small when, obtained final product PDA CP-
DOX-PEG。
In step (1), the ethyl alcohol, distilled water, Dopamine hydrochloride, the ratio of ammonium hydroxide is (20-30) mL:(20-30)
mL:(0.4-0.6)g：(1-3)mL.
In step (2), the PDA of the step (1), zinc nitrate hexahydrate, BBDC, BTC, DMF, the ratio of absolute ethyl alcohol is
(80-120)mg:(40-60)mg:(7-9)mg:(7-9)mg:(10-15)mL:(10-15)mL。
In step (2), the temperature of the hydro-thermal polymerisation is 100-140 DEG C, when the time is 6-24 small.
In step (4), the ratio of PDA the@CP, DOX, PEG-NHS-PDA, PBS of the step (3) are (80-120) mg:
(8-12)mg:(30-50)mg:(20-30)mL。
The concentration of the doxorubicin hydrochloride aqueous solution is 1.3mg/mL.
Dynamic ph response chain prepared by the present invention is based on borate type metallo-organic complex PDA@CP-DOX-PEG, is used for
It identifies the sialic acid of cancer cell surfaces, and inhibits the purposes of the growth of cancer cell by heat-therapeutic action.
Beneficial effects of the present invention：
The product responds chain based on borate type metallo-organic complex pharmaceutical carrier by preparing a kind of dynamic ph, belongs to biology
Medicine functional material preparing technical field introduces borate type organic ligand by preparing metallo-organic complex, and modifies upper one
Layer PEG-NHS-PDA shells have near-infrared thermo-responsive, bio-compatible performance and excellent pH response performances, can be effective
It identifies the sialic acid of cancer cell surfaces, and growth of cancer cells is inhibited by heat-therapeutic action.
Description of the drawings
A, b, c are respectively the PDA in embodiment 1 in Fig. 1, the TEM image of PDA@CP and PDA@CP-DOX-PEG materials.
A, b, c are respectively the PDA in embodiment 1 in Fig. 2, the dynamic light scattering of PDA@CP and PDA@CP-DOX-PEG materials
(DLS) spectrogram.
Fig. 3 be embodiment 1 in PDA, the XPS spectrum figure of PDA@CP and PDA@CP-DOX-PEG materials.
Fig. 4 is PDA, the infrared spectrum of PDA@CP and PDA@CP-DOX-PEG materials.
Fig. 5 is the medicament slow release graph under condition of different pH of the PDA@CP-DOX-PEG materials in experimental example 1.
Fig. 6 be experimental example 1 in DOX, PDA@CP-DOX and PDA@CP-DOX-PEG materials Different Organs in mouse body
Fluorescent optics photo pictorial diagram.
Fig. 7 is the DOX in experimental example 1, and the mean fluorecence of the thermotherapy of PDA@CP-DOX and PDA@CP-DOX-PEG materials is strong
Spend spectrogram Different Organs in mouse body.
Specific embodiment
Adriamycin absorption carriage and long-term sustained release performance testing method described in above-mentioned technical proposal are specially：
(1) long-term sustained release adriamycin behavioral study：
Dynamic ph responds release dynamics (10 of the chain based on borate type metallo-organic complex pharmaceutical carrier release adriamycin
Milligram) in the buffer solution of 20 milliliters of different pH value (pH=5.5,6.5,7.4) is measured, water bath with thermostatic control mild or moderate is trembled at 37 DEG C
Dynamic (120 revs/min).In predetermined time interval, collect 0.1 milliliter of buffer solution and add in 0.2 milliliter of fresh release buffering
Liquid.The burst size of medicine assay drug is detected in 480nm by UV-VIS spectrophotometry, it is every at 0-0.03 milligrams
Milliliter concentration range in adriamycin standard correction figure come determine discharge DOX concentration.According to as a result, calculating accumulation adriamycin
Burst size：
Wherein MtIt is the burst size that adriamycin is in time t, M is the total burst size of adriamycin.
It is described further with reference to specific implementation example and Figure of description.
Embodiment 1：
The ethyl alcohol of 20mL and the distilled water of 20mL are mixed first, 0.4g Dopamine hydrochlorides is then added, and uses magneton
It is dispersed with stirring 20min；Obtained solution is slowly added to the ammonia spirit of 1mL thereto under the constant agitation of 200rpm
(28%-30%), solution become dark brown from yellow immediately and continuously stir 12 it is small when, and be cleaned multiple times with distilled water, and
When drying 12 is small under the conditions of 50 degree, so as to which poly-dopamine nano particle (PDA) be prepared；Then the 80mg that will be prepared into
PDA, 40mg zinc nitrate hexahydrate, the absolute ethyl alcohol of 10mL, the n,N-Dimethylformamide (DMF) of 10mL are added to polytetrafluoroethyl-ne
Among the reaction ax of alkene, then add in 7mg BBDC and 7mg BTC, and in air dry oven hydro-thermal polymerization 6 it is small when 100
DEG C, it is then cooled to room temperature, is cleaned repeatedly with distilled water, finally dried under 50 degrees Celsius of vacuum, then repeat the above steps 3
It is secondary, PDA@CP are prepared.Then obtained PDA@CP are added to the solution of the doxorubicin hydrochloride (DOX, 1.3mg/mL) of 8mg
It is middle stand 12 it is small when, the PDA CP-DOX being then prepared are cleaned multiple times with distilled water.Then the PDA@CP-DOX of 80mg and
(20mM, pH=8.5) and mechanical agitation 12h in the PBS buffer solutions for the 20mL that the PEG-NHS-PDA of 30mg is added to, then
Distillation washing 3 times.The PDA CP-DOX-PEG finally obtained are when drying 12 is small under 30 degree of vacuum.
Embodiment 2：
The ethyl alcohol of 25mL and the distilled water of 25mL are mixed first, 0.5g Dopamine hydrochlorides is then added, and uses magneton
It is dispersed with stirring 30min；Obtained solution is slowly added to the ammonia spirit of 2mL thereto under the constant agitation of 300rpm
(28%-30%), solution become dark brown from yellow immediately and continuously stir 24 it is small when, and be cleaned multiple times with distilled water, and
When drying 24 is small under the conditions of 60 degree, so as to which poly-dopamine nano particle (PDA) be prepared；Then the 100mg that will be prepared into
PDA, 50mg zinc nitrate hexahydrate, the absolute ethyl alcohol of 12.5mL, the n,N-Dimethylformamide (DMF) of 12.5mL are added to poly- four
Among the reaction ax of vinyl fluoride, then add in 8mg BBDC and 8mg BTC, and in air dry oven hydro-thermal polymerization 12 it is small when
It at 120 DEG C, is then cooled to room temperature, is cleaned repeatedly with distilled water, finally dry, then repeat above-mentioned under 60 degrees Celsius of vacuum
PDA@CP are prepared in step 3 time.Then obtained PDA@CP are added to doxorubicin hydrochloride (DOX, the 1.3mg/ of 10.5mg
ML when standing 24 is small in solution), the PDA CP-DOX being then prepared are cleaned multiple times with distilled water.Then take 100mg's
(20mM, pH=8.5) and machinery in the PBS buffer solutions for the 25mL that the PEG-NHS-PDA of PDA@CP-DOX and 40mg are added to
For 24 hours, then distillation is washed 3 times for stirring.The PDA CP-DOX-PEG finally obtained are when drying 24 is small under 40 degree of vacuum.
Embodiment 3：
The ethyl alcohol of 30mL and the distilled water of 30mL are mixed first, 0.6g Dopamine hydrochlorides is then added, and uses magneton
It is dispersed with stirring 40min；Obtained solution is slowly added to the ammonia spirit of 3mL thereto under the constant agitation of 400rpm
(28%-30%), solution become dark brown from yellow immediately and continuously stir 48 it is small when, and be cleaned multiple times with distilled water, and
When drying 48 is small under the conditions of 70 degree, so as to which poly-dopamine nano particle (PDA) be prepared；Then the 120mg that will be prepared into
PDA, 60mg zinc nitrate hexahydrate, the absolute ethyl alcohol of 15mL, the n,N-Dimethylformamide (DMF) of 15mL are added to polytetrafluoroethyl-ne
Among the reaction ax of alkene, then add in 9mg BBDC and 9mg BTC, and in air dry oven hydro-thermal polymerization 24 it is small when
It 140 DEG C, is then cooled to room temperature, is cleaned repeatedly with distilled water, finally dried under 60 degrees Celsius of vacuum, then repeat above-mentioned step
Rapid 3 times, PDA@CP are prepared.Then obtained PDA@CP are added to the doxorubicin hydrochloride (DOX, 1.3mg/mL) of 12mg
When standing 48 is small in solution, the PDA CP-DOX being then prepared are cleaned multiple times with distilled water.Then the PDA@of 120mg are taken
(0mM, pH=8.5) and mechanical agitation in the PBS buffer solutions for the 30mL that the PEG-NHS-PDA of CP-DOX and 50mg is added to
48h, then distillation washing 3 times.The PDA CP-DOX-PEG finally obtained are when drying 48 is small under 50 degree of vacuum.
Test example 1：Release and thermotherapy performance study
(1) release dynamics of the dynamic ph response chain based on borate type metallo-organic complex pharmaceutical carrier release adriamycin
(10 milligrams) measure (pH=5.4,6.5,7.4) in the buffer solution of 25 milliliters of different pH value, light in water bath with thermostatic control at 37 DEG C
Degree shake (120 revs/min).In predetermined time interval, collect 0.2 milliliter of buffer solution and add in 0.1 milliliter of fresh release
Buffer solution.The burst size of medicine assay drug is detected in 480nm by UV-VIS spectrophotometry, in 0-0.03 millis
The standard correction figure of adriamycin in gram every milliliter of concentration range determines the DOX concentration of release.According to as a result, calculate accumulation Ah
Mycin burst size.
Fig. 5 the result shows that：Adriamycin responds chain releasing based on borate type metallo-organic complex pharmaceutical carrier in dynamic ph
It puts with the reduction of pH and increases, and excellent long-term releasability is presented.Dynamic ph responds chain in the buffer solution of pH=5.4
3.4% adriamycin is only discharged in preceding 2 hours based on borate type metallo-organic complex pharmaceutical carrier, and is reached after 1 day
Sustained release balance.
(2) imaging experiment 80mm has been carried out when tumour reaches3Left and right.These mouse are by intravenous injection DOX, PDA@CP-
DOX and PDA@CP-PEG-DOX.After 24 hours, tumor locus is irradiated to 1.5W cm with 808nm laser-2, continue 5 minutes.Temperature
Degree variation and infrared chart record image camera by infrared chart.
Fig. 6 the result shows that：When 4 is small, both PDA CP-DOX and PDA CP-PEG-DOX are aobvious in liver
Less fluorescence is shown, but more fluorescence can be shown in tumour, it is thin that this shows that medicine carrying material can be attached to cancer
Cellular surface.After being injected when 24 is small, increased fluorescence signal detects PDA CP-DOX and PDA CP-PEG- in tumor tissues
DOX, and DOX does not show fluorescence.We can find PDA@CP-PEG-DOX and most aggregate amounts is shown during detection
In inside tumor than PDA@CP-DOX and DOX.
(3) drug and various kinds of drug carrier (DOX, PDA@CP-DOX and PDA@CP-PEG-DOX difference are injected by tail
Pharmaceutical carrier is injected with the dosage of the rat tail of 5mg/Kg.After being acted on when 4 and 24 is small in mouse body, in automatic live body body
Imaging system imaging machine carries out fluorescence intensity test to the heart of excision, liver, spleen, lung, kidney and tumor tissues.
Fig. 7 the result shows that：When 4 is small, do not distinguished significantly in the fluorescence intensity of each histoorgan, when to
Up to 24 it is small when, in tumor tissues, PDA CP-PEG-DOX can have other contrast materials of higher fluorescence intensity ratio.
By the image of Fig. 1 it is observed that comparison PDA and PDA@CP, PDA@CP polymer layer more than PDA, explanation
Metallo-organic complex successful deposition is to PDA surfaces, when introducing molecule PEG-NHS-PDA, it can be found that PDA@CP-PEG-DOX
Surface than PDA@CP becomes more coarse, illustrates that PDA@CP-PEG-DOX are successfully successfully prepared.
By the image of Fig. 2 it is observed that dynamic light scattering (DLS) spectrogram is it can be found that grain size becomes increasing,
PDA, the average diameter of PDA@CP and PDA@CP-PEG-DOX are 197.4,222.3 and 242.0 nanometers respectively.Show PEG-NHS-
PDA successfully gathers the surface of PDA@CP.
By the image of Fig. 3 it is observed that the infrared spectrum of PDA, PDA@CP and PDA@CP-DOX-PEG materials.PDA's
Infrared spectrum nano particle shows the peak value about 1624 and 1530cm of two kinds of typical indoles-1, show the successful system of PDA
It is standby.After CP depositions, typical C=O stretching vibrations carboxylic acid (1737cm-1) and B-O phenyl boric acids (1389cm-1) appear in
In the infrared spectrum of PDA@CP and PDA@CP-PEG nano-particles, show (BBDC) and BTC and be successfully introduced into polymer
In the middle of preparation.
By the image of Fig. 4 it is observed that the XPS spectrum figure of PDA, PDA@CP and PDA@CP-DOX-PEG materials.In XPS light
In spectrum we can clearly find B1s typical peak (189.2eV) and Zn2p (1021.9eV) on PDA@CP surfaces,
Show BBDC and BTC and zinc ion concerted reaction.But the peak value PDA@CP-PEG of B1s and Zn2p are almost disappeared, surface table
There is a thick layer polymer layer PEG-NHS-PDA in face.
Claims (6)
1. a kind of dynamic ph responds preparation method of the chain based on borate type metallo-organic complex, which is characterized in that including as follows
Step：
(1) ethyl alcohol and distilled water are mixed first, then adds Dopamine hydrochloride, and 20-40min is dispersed with stirring with magneton；
Obtained solution is slowly added to ammonia spirit (28%-30%), solution is immediately thereto under the constant agitation of 200-400rpm
Become dark brown from yellow and continuously stir 12-48 it is small when, and be cleaned multiple times with distilled water, and dried under the conditions of 50-70 DEG C
When 12-48 is small, so as to which poly-dopamine nano particle (PDA) be prepared；
(2) by PDA obtained by step (1), zinc nitrate hexahydrate, absolute ethyl alcohol, n,N-Dimethylformamide (DMF) is added to poly-
Among the reaction ax of tetrafluoroethene, 3,5- dicarboxyphenyi boric acid BBDC and 1,3,5- Trimesic acid BTC are then added in, and
Hydro-thermal polymerisation in air dry oven, is then cooled to room temperature, and is cleaned repeatedly with distilled water, finally at 50-70 DEG C of vacuum
Drying, is prepared prepared-PDA@CP (P-PDA@CP)；
(3) according to step (2) step, by P-PDA@CP and zinc nitrate hexahydrate, absolute ethyl alcohol, DMF, BBDC, BTC is again
Hydro-thermal polymerisation is carried out, is cleaned, drying；The hydro-thermal polymerisation is repeated 3 times；Obtain PDA@CP；
(4) by the PDA CP that step (3) obtains be added to doxorubicin hydrochloride (DOX) aqueous solution stand 12-48 it is small when, then prepare
Obtained PDA@CP-DOX are cleaned multiple times with distilled water, and then PDA@CP-DOX are added to the biological chain of polyethylene glycol-dopamine
(PEG-NHS-PDA) (20mM, pH=8.5) and mechanical agitation 12-48h in PBS buffer solutions, then distillation washing 3 times；Most
The PDA CP-DOX-PEG obtained afterwards dried at 30-50 DEG C of vacuum 12-48 it is small when；Obtained final product dynamic ph response chain
Based on borate type metallo-organic complex PDA@CP-DOX-PEG.
2. a kind of dynamic ph response preparation method of the chain based on borate type metallo-organic complex as described in claim 1,
It is characterized in that, in step (1), the ethyl alcohol, distilled water, Dopamine hydrochloride, the ratio of ammonium hydroxide is (20-30) mL:(20-30)
mL:(0.4-0.6)g：(1-3)mL.
3. a kind of dynamic ph response preparation method of the chain based on borate type metallo-organic complex as described in claim 1,
It is characterized in that, in step (2), the PDA of the step (1), zinc nitrate hexahydrate, BBDC, BTC, DMF, the ratio of absolute ethyl alcohol
For (80-120) mg:(40-60)mg:(7-9)mg:(7-9)mg:(10-15)mL:(10-15)mL.
4. a kind of dynamic ph response preparation method of the chain based on borate type metallo-organic complex as described in claim 1,
It is characterized in that, in step (2), the temperature of the hydro-thermal polymerisation is 100-140 DEG C, when the time is 6-24 small.
5. a kind of dynamic ph response preparation method of the chain based on borate type metallo-organic complex as described in claim 1,
It is characterized in that, in step (4), PDA@CP, DOX, PEG-NHS-PDA that the step (3) obtains, the ratio of PBS is (80-
120)mg:(8-12)mg:(30-50)mg:(20-30)mL；Wherein, the concentration of the doxorubicin hydrochloride aqueous solution is 1.3mg/
mL。
6. dynamic ph response chain made from preparation method described in Claims 1 to 5 is based on borate type metallo-organic complex
PDA@CP-DOX-PEG for identifying the sialic acid of cancer cell surfaces, and inhibit the growth of cancer cell by heat-therapeutic action
Purposes.
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| CN112094416A (en) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN116139296A (en) * | 2023-02-27 | 2023-05-23 | 河南大学 | MOF (metal oxide fiber) medicine carrying material modified by yam polysaccharide and having glucose responsiveness as well as preparation method and application thereof |
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| XIAOYAN ZHONG等: ""Polydopamine as a Biocompatible Multifunctional Nanocarrier for Combined Radioisotope Therapy and Chemotherapy of Cancer"", 《ADV. FUNCT. MATER.》 * |
| 何旺龙等: ""多巴胺修饰聚乙二醇的合成及与 Fe3+配位研究"", 《井冈山大学学报(自然科学版)》 * |
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| CN109985247A (en) * | 2019-04-03 | 2019-07-09 | 河南科技学院 | A kind of preparation method of the hybridized metal organic framework compounds for drug release |
| CN112094416A (en) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN112094416B (en) * | 2020-09-23 | 2022-04-26 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN116139296A (en) * | 2023-02-27 | 2023-05-23 | 河南大学 | MOF (metal oxide fiber) medicine carrying material modified by yam polysaccharide and having glucose responsiveness as well as preparation method and application thereof |
| CN116139296B (en) * | 2023-02-27 | 2023-08-22 | 河南大学 | MOF (metal oxide fiber) medicine carrying material modified by yam polysaccharide and having glucose responsiveness as well as preparation method and application thereof |
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