CN105251420A - Preparation method for multifunctional composite microspheres - Google Patents
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Abstract
The invention provides a preparation method for multifunctional composite microspheres. Through introduction of natural high polymers, a solvothermal method is employed to synthesize functional magnetic nanoparticles and carbon quantum dots synchronously, the surfaces of the magnetic nanoparticles are coated with a metal-organic framework material, according to surface porous structure and charge difference, and the fluorescent carbon quantum dots are connected successfully through electrostatic adsorption and physical adsorption. The fluorescence quenching effect of the magnetic nanoparticles to carbon quantum dots is overcome, the material specific surface area is raised, and the pH response performance is given to the material. The multifunctional integrated composite material can be used in fields of catalysis, adsorption and immunodetection, targeting treatment, cell separation and the like in medical science.
Description
Technical field
That the present invention relates to is a kind of preparation method of drug bearing microsphere material, is specifically related to the preparation method of the multi-functional complex microsphere carrier material of a kind of magnetic-light-pH response-high-specific surface area.
Background technology
1, preparation has the importance of multifunctional material of high drug load, fluorescent tracing and special target administration.
Cancer harm in the world just constantly aggravates, and serious threatens the healthy of the mankind.The maximum cancer treatment method of present stage clinical middle use is operation and traditional chemotherapy.Chemotherapy is mainly through Formulations for systemic administration mode Therapeutic cancer, and namely medicine enters blood circulation by medicine-feeding part, is transported to each organs and tissues by the circulatory system.But, water-soluble and the less stable of major part antineoplastic, cause the bioavilability of medicine low, nearly all conventional Effective Anti cancer drug all has larger toxicity, can not distinguish between tumor cells and normal cell effectively in cancer treatment procedure, the normal cell at non-active position can be killed thus produce very strong toxic and side effect, meanwhile, cannot monitor medicine and locate again, in the distributed process of medicine, a large amount of medicine of organism metabolism, reduces the bioavilability of medicine, again because of under pathological state, oncogenic special microenvironment is led in the change of the pH gradient in cell and between extracellular environment, compared with the pH=7.4 of the circulatory system, obvious slant acidity in solid tumor, and utilize this tumour-specific, pH responsive materials is applied to the special target function caused by tumor microenvironment, the object of pH response medicine controlled release can be reached, not only can reduce the toxic and side effect of agents on normal cells tissue, the drug concentration of tumor locus can also be increased, especially combine with other special target functions, cooperative effect can be produced, the increase medicine stability of high degree, extenuate drug degradation, cell endocytic and intracellular delivery is promoted at tumor locus, realize medicine to discharge in a large number.Therefore, in order to ensure specificity, kill tumour cell efficiently, simultaneously again can the normal histoorgan of damage of minimum degree, carry out there is high drug load, the research of multifunctional anticancer pharmaceutical carrier of fluorescent tracing and special target administration is extremely important for the treatment of cancer.
In order to effective Therapeutic cancer, the design of multifunctional carrier material seems particularly important, especially while the certain drugloading rate of guarantee and good biological security, expandable carrier material functional, the material with functions such as fluorescence, magnetic responsiveness, pH responses is integrated in a carrier system, make the variation of single carrier material practical function, thus realize that fluorescence imaging detects, medicine controlled delivery and treatment of cancer synchronously carry out.
2, prior art combination is difficult to prepare and has high drug load, fluorescent tracing and the multifunctional material magnetic material of special target administration and the combination of fluorescent material usually because lattice does not mate, or Size Distribution is difficult to regulation and control, preparation technology's repeatability is poor, especially magnetic nano-particle because of light absorption and electro transfer comparatively serious to the Fluorescence quenching effect of fluorescent material, these combinations that all result in magnetic material and fluorescent material are difficult.
Between pH response material and magnetic nanoparticle, if interior coated magnetic nanoparticle can reduce the magnetic responsiveness of material, if outer carried magnetic nano particle can weaken the pH response of material itself, result in choosing of combining form therebetween more difficult; Drugloading rate and pH respond between carrier material and are also difficult to reach an agreement, the macromolecular material with special chemical key is generally at present for pH response medicine carrier material, mainly through in acid condition, the fracture controlling to be formed with drug molecule chemical bond reaches required pH response, the while of ensureing that other are functional if want, in coated meeting occupy medicine space, outer load because of its specific area usually less, the drugloading rate of material all can be caused to reduce; If it is extremely difficult to combine four, not only need to overcome each other in conjunction with obstacle, also need the pattern after considering several functions Material cladding, particle diameter and dispersed control, and the guarantee of material water dissolution properties and biological safety, prevent capillary embolism, the problems such as whole body effective medicine concentration difference is larger limit the clinical medical effect of material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method integrating the multi-functional multi-functional complex microsphere such as magnetic, light, pH response and high-specific surface area.
The object of the present invention is achieved like this:
Step one: synchronized compound functionalization-Fe
3o
4microsphere substrate and carbon quantum dot,
1 ~ 2g Iron(III) chloride hexahydrate is dissolved in 50 ~ 100mL ethylene glycol, dissolve completely, add 3.5 ~ 4.5g ammonium acetate and stir, add natural polymers, again stir and be transferred in hydrothermal reaction kettle, 180 ~ 220 DEG C of reactions are after 10 ~ 14 hours, and room temperature is down in cooling naturally; Centrifugally get supernatant liquor A and lower sediment B respectively; Supernatant liquor A dialyses purifying, and freeze drying 48h obtains the short grained carbon quantum dot of functionalization, is scattered in ethanol, and being configured to concentration is 30 ~ 50mg/L solution C, stores for future use at 4 DEG C; Lower sediment B respectively cleans 3 times with deionized water and absolute ethyl alcohol respectively, 60 DEG C of vacuum drying 8 ~ 12 hours, the magnetic microsphere D of obtained functionalization;
Step 2: the coated functionalization of synthesis MOFs-Fe
3o
4nucleocapsid structure microballoon,
By the magnetic microsphere D ultrasonic disperse of 50 ~ 150mg functionalization in appropriate solvent, adding according to mol ratio is respectively 1:0.5 ~ 2 slaine and organic ligand, the magnetic microsphere D of functionalization and the amount ratio of organic ligand are 50 ~ 150mg:2 ~ 10mmol, react 20 ~ 40 minutes at oil bath 60 ~ 160 DEG C, the magnetic field that products therefrom utilizes additional magnet to produce is separated, repeatedly clean with absolute ethyl alcohol and solvent respectively, remove residual precursors, then vacuum drying 12 hours at 120 ~ 150 DEG C, obtained magnetic metal organic framework composite material Fe
3o
4mOFs;
Step 3: synthesis Fe
3o
4mOFsCDs nucleocapsid structure microballoon,
By the Fe of 50 ~ 150mg step 2 gained
3o
4mOFs is scattered in 25 ~ 100mL solution C, and be placed in constant temperature oscillator vibration 12 ~ 48h, magnetic field that products therefrom utilizes additional magnet to produce is separated, and cleans 3 times with ethanolic solution, and 60 DEG C of vacuum drying 12 hours, namely obtain multi-functional composite microsphere material.
The present invention can also comprise:
1, described natural polymers is shitosan or sodium carboxymethylcellulose or Carboxylic Acid Fibre element or potassium carboxymethylcellulose or sodium carboxymethylcellulose potassium.
2, slaine is zinc nitrate.
3, described organic ligand is M-phthalic acid, terephthalic acid (TPA) or Trimesic acid.
4, described solvent is DMF.
5, the mass ratio of natural polymers and Iron(III) chloride hexahydrate is 1:2.
The invention provides the synthetic method of the multi-functional complex microsphere of a kind of magnetic-light-pH response-high-specific surface area.Multifunctional carrier material of the present invention take natural polymers as stabilizing agent, adopts solvent-thermal method synchronized compound functional magnetic particle and carbon quantum dot, with magnetic particle Fe
3o
4for core, metallic organic framework composite (MOFs) is Shell Materials, with carbon quantum dot (CDs) for fluorescent material, has successfully prepared magnetic Fe by in-stiu coating method
3o
4mOFsCDs composite.
The magnetic nano-particle that overcomes of the present invention, to carbon quantum dot fluorescent quenching effect, improves the specific area of material, also gives material pH response performance.The composite of the multifunctional all of gained can be applicable to the field such as immune detection, targeted therapy, cell separation in catalysis, absorption and medical science.
Feature of the present invention and beneficial effect are mainly reflected in:
1, the present invention adopts the magnetic microsphere that solvent-thermal method obtains, and adds natural polymers, synchronized compound functionalized magnetic microsphere and carbon quantum dot in building-up process.The method is better dispersed, be convenient to next step coated, and only under high-temperature and high-pressure conditions, carbon source pyrolysis can synthesize carbon quantum dot fast, ethylene glycol is reducing agent simultaneously, ammonium acetate is that alkali source and pore-foaming agent are all absolutely necessary, along with the pyrolysis of ammonium acetate, discharge ammonia bubble gradually, do not add the natural polymer period of the day from 11 p.m. to 1 a.m, finally can form ganoid hollow magnetic microsphere, and introduce the good natural polymer of histocompatbility not only can as stabilizing agent, suppress the reunion of magnetic nano-particle, getting rid of ammonia bubble makes magnetic nano-particle self assembly be shaggy nano particle cluster, ensure the superparamagnetism of magnetic nanoparticle, for double-mode imaging is in the future provided fundamental basis, under the solvent thermal reaction condition of HTHP, as the carbon source of synthesis carbon quantum dot, pyrolysis can also be there is, reaches the object of the two synchronized compound.Simultaneously because its surface has different functional groups, functional modification can be carried out to magnetic nano-particle and carbon quantum dot to a certain extent, be convenient to next step reaction and carry out.
2, the present invention adopts carbon quantum dot to be fluorescent material.In contrast to other fluorescent materials, carbon quantum dot preparation technology is simple, cheap, itself is nontoxic, heavy metal ion enrichment in vivo can not be produced, impact is clearly had on the growth of cell and survival, there is good biocompatibility and biological safety, improve the realizability of clinical practice.The functionalized carbon quantum dot obtained by the present invention can enter cell, can inspire the fluorescence of different colours under different excitation wavelength, can use as biological developing agent separately.
3, the present invention adopts between magnetic material and carbon quantum dot, introduces metal-organic framework materials (MOFs) as MAGNETIC BASEMENT clad material.MOFs is the crystalline material with space periodicity network structure be self-assembled into by coordinate bond by metal ion and multi-functional organic ligand.MOFs is introduced in structure, functionalization is carried out to MAGNETIC BASEMENT surface coated, overcome between magnetic material and fluorescent material in conjunction with problem, the Fluorescence quenching effect of magnetic nano-particle to quantum dot can be reduced, improve the luminous intensity of carbon quantum dot.Because of it, there is the features such as bigger serface, pore size is adjustable simultaneously, by regulating response parameter, reaching the Modulatory character of magnetism of material and specific area, thus increase carrier drugloading rate; Again because of outer load carbon quantum dot, improve the biocompatibility of MOFs, and material also has certain pH sensitiveness, under the weak acid microenvironment of tumour, carrier material generation chemical bond rupture or degraded promote drug diffusion, improve local organization drug concentration, reduce times of injecting drug, strengthen result for the treatment of.
4, the present invention adopts in-stiu coating method when introducing MOFs structure, usually Self assembly method is all adopted when synthesizing MOFs structure, the method complex process and length consuming time, needs repeatedly circulate coated, and it is easy to be coated uneven, product morphology also cannot be determined, and in-stiu coating method is and carries out in-situ precipitate MOFs structure at substrate surface, directly by regulating reaction ratio, utilize central metallic ions and the synthesis of organic ligand in-situ deposition, technique is simple consuming time short, also overcome pattern in several functions Material cladding process simultaneously, particle diameter and dispersed control problem.
Accompanying drawing explanation
Fig. 1 is the functionalization Fe that embodiment 1 obtains
3o
4, Fe
3o
4mOFs and Fe
3o
4x-ray diffraction (XRD) figure of MOFsCDs.
Fig. 2 is the Fe that embodiment 1 obtains
3o
4the utilizing emitted light spectrogram of MOFsCDs under different excitation wavelength.
Detailed description of the invention
Illustrate below and the present invention is described in more detail.
Embodiment 1
Step (1) synchronized compound functionalization-Fe
3o
4microsphere substrate and carbon quantum dot,
1.35g Iron(III) chloride hexahydrate is dissolved in 70mL ethylene glycol, dissolves completely, add 3.85g ammonium acetate and stir, add natural polymers, be transferred to after again stirring in hydrothermal reaction kettle, 180-220 DEG C of reaction is after 10-14 hour, and room temperature is down in cooling naturally.Centrifugally get supernatant liquor A and lower sediment B respectively; A dialyses purifying, and freeze drying 48h obtains the short grained carbon quantum dot of functionalization, is scattered in ethanol, and being configured to concentration is 40mg/L solution C, stores for future use at 4 DEG C; B respectively cleans 3 times with deionized water and absolute ethyl alcohol respectively, 60 DEG C of vacuum drying 8-12 hour, the magnetic microsphere D of obtained functionalization.
The coated functionalization of step (2) synthesis MOFs-Fe
3o
4nucleocapsid structure microballoon
By 100mgD ultrasonic disperse in solvent, adding according to mol ratio is respectively 1:1 slaine and organic ligand, and the amount ratio of D and organic ligand is 100mg:5mmol, reacts 20-40 minute at oil bath 60-160 DEG C.Magnetic field that products therefrom utilizes additional magnet to produce is separated, and repeatedly cleans respectively with absolute ethyl alcohol and solvent, removes the precursors remained, and then vacuum drying 12 hours under 120-150 ° of C, can obtain magnetic metal organic framework composite material Fe
3o
4mOFs.
Step (3) synthesis Fe
3o
4mOFsCDs nucleocapsid structure microballoon
By the Fe of step (2) gained
3o
4mOFs (100mg) is scattered in 25-100mLC, be placed in constant temperature oscillator to vibrate 12-48h, the magnetic field that products therefrom utilizes additional magnet to produce is separated, and cleans 3 times with ethanolic solution, 60 DEG C of vacuum drying 12 hours, namely obtain multi-functional composite microsphere material.
Step (1) synchronized compound functionalized carbon quantum dot, dialysis purifying can improve quantum dot concentration; Because carbon quantum dot is undersized, be scattered in liquid and cannot be separated, freeze drying can improve product yield; 4 DEG C of preservations are conventional preservation conditions of medical material; Must disperse in ethanol, to avoid in step 3, the introducing of the aqueous solution makes MOFs structure destroy.
Step (1), (2) and (3) vacuum drying can prevent tri-iron tetroxide oxidized, retain the magnetic of product.
Embodiment 2
On the basis of embodiment 1: the optimum quality ratio of natural polymers and Iron(III) chloride hexahydrate elects 1:2 as.
Natural polymers content is low, and cause functionalization incomplete, the carbon quantum dot content of synchronized compound is few; Natural polymers content height can cause Magnetic Isolation effect poor, and also there will be the excessive pattern caused of macromolecule introducing and be cross-linked, the particle diameter heterogeneity needed for pharmaceutical carrier, pattern are poor.
Embodiment 3
On the basis of embodiment 2: hydrothermal temperature elects 200 DEG C as, react 12 hours.The control of temperature and reaction time parameter, can improve the uniform particle diameter of pharmaceutical carrier further.The best polydispersity index of its product can reach 0.154-0.332, particle size narrow distribution is described, favorable dispersibility.
Embodiment 4
On the basis of embodiment 3: the natural polymers added elects shitosan or sodium carboxymethylcellulose or Carboxylic Acid Fibre element or potassium carboxymethylcellulose or sodium carboxymethylcellulose potassium as.
Different natural polymers has different functional groups and surface potential as the MAGNETIC BASEMENT of carbon source synchronized compound and quantum dot surface, simplifies functionalized modification step, is also convenient to next step reaction.Shitosan is carbon source synthetic surface with the amination modified magnetic substrate of positive charge and carbon quantum dot, by the electrostatic interaction between substrate and organic ligand, is conducive to outer load MIL type MOFs structure; Other carboxylated cellulose elements are carbon source synthetic surface with the carboxylated MAGNETIC BASEMENT of negative electrical charge and carbon quantum dot, by the electrostatic interaction between substrate and metal ion, are conducive to outer load MIL, ZIF type MOFs structure; And the biological safety of synthesized difference in functionality MAGNETIC BASEMENT and carbon quantum dot is all better, can not need further functionalization, enter human body as drug carrier material directly separately separately.
Embodiment 5
On the basis of embodiment 4: in step (2), slaine elects zinc nitrate as.
Zinc ion, to human non-toxic, is needed by human body metallic element, and the degradation process of material can not have side effects to human body, and Zn complex color mostly is white, can reduce the quenching effect that magnetic checks carbon quantum dot further.
Embodiment 6
Difference from Example 5 is: it is shitosan that step (1) adds natural polymers; Step (2) solvent is N, dinethylformamide, slaine is zinc nitrate, organic ligand is M-phthalic acid, terephthalic acid (TPA), Trimesic acid, and reaction temperature is 140 DEG C, and the reaction time is 40min, vacuum drying 150 DEG C of 12h, solvent boiling point, product is respectively with absolute ethyl alcohol and DMF cleaning.
This embodiment prepares MIL type MOFs material, and its specific area can reach 427m
2/ more than g.Reaction time, too short meeting caused not exclusively coated, and the reaction time longly can be cross-linked, and cannot ensure the dispersiveness of product.The drugloading rate of final combination product is greater than 83.67mg/g, and medicine carrying efficiency is for being greater than 89.7%.
Embodiment 7
Difference from Example 5 is: it is sodium carboxymethylcellulose or Carboxylic Acid Fibre element or potassium carboxymethylcellulose or sodium carboxymethylcellulose potassium that step (1) adds natural polymers; Step (2) solvent is methyl alcohol, and slaine is zinc nitrate, organic ligand methylimidazole, and reaction temperature is 70 DEG C, and the reaction time is 20min, and vacuum drying 120 DEG C of 12h products use absolute ethyl alcohol and washed with methanol respectively.
The present embodiment prepares ZIF type MOFs material, and its specific area is up to 1295m
2/ g.Reaction time, too short meeting caused not exclusively coated, and the reaction time longly can be cross-linked, and cannot ensure the dispersiveness of product.The drugloading rate of final combination product is 141.75mg/g, and medicine carrying efficiency is 94.5%.
Embodiment 8
Difference from Example 6 is: step (3) is scattered in 50mLC, is placed in constant temperature oscillator and vibrates 24h.
Above addition adjustment, recording best fluorescence intensity by XRF is 2-5 × 10
5(excitation wavelength is 360nm).
Embodiment 9
Difference from Example 7 is: step (3) is scattered in 50mLC, is placed in constant temperature oscillator and vibrates 24h.
Above addition adjustment, recording best fluorescence intensity by XRF is 7-9 × 10
5(excitation wavelength is 360nm).
Claims (5)
1. a preparation method for multi-functional complex microsphere, is characterized in that:
Step one: synchronized compound functionalization-Fe
3o
4microsphere substrate and carbon quantum dot,
1 ~ 2g Iron(III) chloride hexahydrate is dissolved in 50 ~ 100mL ethylene glycol, dissolve completely, add 3.5 ~ 4.5g ammonium acetate and stir, add natural polymers, again stir and be transferred in hydrothermal reaction kettle, 180 ~ 220 DEG C of hydro-thermal reactions are after 10 ~ 14 hours, and room temperature is down in cooling naturally; Centrifugally get supernatant liquor A and lower sediment B respectively; Supernatant liquor A dialyses purifying, and freeze drying 48h obtains the short grained carbon quantum dot of functionalization, is scattered in ethanol, and being configured to concentration is 30 ~ 50mg/L solution C, stores for future use at 4 DEG C; Lower sediment B respectively cleans 3 times with deionized water and absolute ethyl alcohol respectively, 60 DEG C of vacuum drying 8 ~ 12 hours, the magnetic microsphere D of obtained functionalization;
Step 2: the coated functionalization of synthesis MOFs-Fe
3o
4nucleocapsid structure microballoon,
By the magnetic microsphere D ultrasonic disperse of 50 ~ 150mg functionalization in appropriate solvent, adding according to mol ratio is respectively 1:0.5 ~ 2 slaine and organic ligand, the magnetic microsphere D of functionalization and the amount ratio of organic ligand are 50 ~ 150mg:2 ~ 10mmol, react 20 ~ 40 minutes at oil bath 60 ~ 160 DEG C, the magnetic field that products therefrom utilizes additional magnet to produce is separated, repeatedly clean with absolute ethyl alcohol and solvent respectively, remove residual precursors, then vacuum drying 12 hours at 120 ~ 150 DEG C, obtained magnetic metal organic framework composite material Fe
3o
4mOFs;
Step 3: synthesis Fe
3o
4mOFsCDs nucleocapsid structure microballoon,
By the Fe of 50 ~ 150mg step 2 gained
3o
4mOFs is scattered in 25 ~ 100mL solution C, and be placed in constant temperature oscillator vibration 12 ~ 48h, magnetic field that products therefrom utilizes additional magnet to produce is separated, and cleans 3 times with ethanolic solution, and 60 DEG C of vacuum drying 12 hours, namely obtain multi-functional composite microsphere material.
2. the preparation method of multi-functional complex microsphere according to claim 1, is characterized in that: described natural polymers is shitosan or sodium carboxymethylcellulose or Carboxylic Acid Fibre element or potassium carboxymethylcellulose or sodium carboxymethylcellulose potassium; Slaine is zinc nitrate; Described organic ligand is M-phthalic acid, terephthalic acid (TPA) or Trimesic acid.
3. the preparation method of multi-functional complex microsphere according to claim 1 and 2, is characterized in that: the mass ratio of natural polymers and Iron(III) chloride hexahydrate is 1:2.
4. the preparation method of multi-functional complex microsphere according to claim 1 and 2, is characterized in that: hydrothermal temperature is 200 DEG C, reacts 12 hours.
5. the preparation method of multi-functional complex microsphere according to claim 3, is characterized in that: hydrothermal temperature is 200 DEG C, reacts 12 hours.
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| CN116144069B (en) * | 2023-02-01 | 2024-04-09 | 上海慧翌新材料科技有限公司 | Polysaccharide-based fluorescence response sponge and preparation method and application thereof |
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