CN102499943B - Preparation and anti-tumor activity of polymer wrapped heteropoly acid nano hybrid material - Google Patents

Preparation and anti-tumor activity of polymer wrapped heteropoly acid nano hybrid material Download PDF

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CN102499943B
CN102499943B CN 201110332673 CN201110332673A CN102499943B CN 102499943 B CN102499943 B CN 102499943B CN 201110332673 CN201110332673 CN 201110332673 CN 201110332673 A CN201110332673 A CN 201110332673A CN 102499943 B CN102499943 B CN 102499943B
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宋宇飞
刘秀丽
张洁
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Beijing University of Chemical Technology
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Abstract

The invention discloses preparation and anti-tumor activity research of a polymer wrapped heteropoly acid nano hybrid material, belonging to the field of a polyacid-based nano hybrid material. The preparation method comprises the following steps: mixing ZnW9 heteropoly acid aqueous solution and polymer PGEA aqueous solution; oscillating, dialyzing and lyophilizing to obtain solid powdery polymer PGEA wrapped ZnW9 heteropoly acid nano hybrid material. According to the preparation method, polymer cation PGEA with good biocompatibility and sandwich-type heteropoly acid functional anion with anti-tumor medicinal value are assembled sequentially to obtain the solid particles of the material; and the toxic effect of the nano-grade hybrid material on tumor cells of a mouse is studied for the first time, and results indicate that the nano-grade hybrid material has high anti-tumor activity, and is a potential anti-tumor medicament. The preparation process of the nano hybrid material is simple, green and pollution-free.

Description

A kind of preparation and anti-tumor activity thereof of polymer parcel heteropoly acid nano-hybrid material
Technical field
The invention belongs to polyacid base nano-hybrid material preparing technical field, particularly a kind of preparation and anti-tumor activity thereof of polymer parcel heteropoly acid nano-hybrid material.
Background technology
Polyacid compound is the poly-metal deoxide that a class contains metals such as V, Mo, W, is extended familys in the inorganic clusters compound.Be same polyanionic by what oxyacid radical ion of the same race condensation formed, isopolyacid is in its acid.Be heteropolyanion by what the condensation of different types of oxyacid root anion formed, heteropoly acid is in its acid.At present known have nearly 70 kinds of atoms of elements to can be used as hetero atom in the heteropoly acid, comprise the first whole serial transition elements, most second and third serial transition elements is added B, Al, Ga, Si, Ge, Sn, P, As, Sb, Bi, Se, Te, I etc.And every kind of hetero atom often can different valence state be present in the heteropolyanion, so kind is quite various.
Polyacid is dissolved in the anion structure that has in the time of can keeping solid-state behind the water, have different electric charges, shape and size simultaneously, be convenient to the carrying out of assembling chemical, after assembling, keep some characteristics of self and be incorporated in the new hybrid material, thereby be widely used in electrochemistry, catalytic chemistry and biomedicine field etc.In recent years the biological activity about polyoxometallate mainly comprises the following aspects: the high selectivity to the enzyme function suppresses the anti-tumor activity of vivo and vitro, antiviral activity and anti-AIDS cytotoxic activity.Wherein along with the hazardness of malignant tumor more and more is familiar with by people, the anti-tumor activity of polyacid and derivant thereof has also obtained increasing concern.
At present, mainly be operative treatment, radiotherapy, chemotherapy and Chinese medicine to tumor treatment.At present the antitumor drug of wide clinical application also majority be non-selective medicine, body is interior widely distributed.In order to improve curative effect of medication, reduce toxic and side effects, people explore its control delivery systme, at present successfully with the multiple polymers material, as liposome, starch etc. and nanoscale polyacid granulometric composition control delivery, and obtain good anti-tumor test result.
Polymer P GEA (poly (2-hydroxyl-3-(2-hydroxyethylamino) propyl methacrylate)) is that a kind of hypotoxicity (is less than 10% of PEI toxicity, branched structure is arranged, 25kDa), high transfection activity (is higher than or is comparable to PEI, 25kDa) the high molecular polymer genophore of water soluble solution.Its chemical constitution is accurate, and has side chain cation secondary amine group and uncharged hydrophilic hydroxyl, and it is that the ring-opening reaction that the amino by the epoxide group of PGMA (poly (glycidyl methacrylate)) and ethanolamine carries out makes.
Utilization has the ZnW of active anticancer 9(molecular formula is Na to heteropoly acid 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O) and the biological nature of water-soluble polymer PGEA (good transfection activity, hypotoxicity), in aqueous solution, both are assembled, can study to obtain bigger using value to its some potential physical and chemical performances and biological antitumor characteristic.
Summary of the invention
The purpose of this invention is to provide a kind of polymer parcel heteropoly acid nano-hybrid material, and its anti-tumor activity is studied.
Technical scheme of the present invention is that (poly (2-hydroxyl-3-(2-hydroxyethylamino) propyl methacrylate) is dissolved in the solution that forms a series of different unit charge concentration in the ultra-pure water to the PGEA that cytotoxicity is extremely low; ZnW 9Heteropoly acid is dissolved in the polyacid solution that forms a series of different unit charge concentration in the ultra-pure water, after both are mixed, obtains colloid solution, stirs, and dialysis namely obtains PGEA and ZnW after the lyophilizing 9The nano-hybrid material of heteropoly acid assembling.
A kind of polymer parcel heteropoly acid nano-hybrid material of the present invention's preparation is specially water-soluble polymer PGEA parcel ZnW 9The heteropoly acid nano-hybrid material, it is the white solid powder; Concentration range with 0.01mol/L-0.1mol/L is dispersed in formation colloidal state solution in the water with it, and through scanning electron microscope and the test of laser particle size scatterometer, the pattern rule is consistent, and scanning electron microscope shows that the solid mean diameter is evenly distributed on 30-100nm; The theoretical general formula of this nano-hybrid material is [M] +[WZn 3(H 2O) 2(ZnW 9O 34) 2/ 12] -, the monomer of M representation polymer PGEA wherein, its structure is shown below,
Figure BDA0000102873440000031
[WZn 3(H 2O) 2(ZnW 9O 34) 2] 12-Be ZnW 9The anion of heteropoly acid; ZnW 9Heteropoly acid is the sandwich type heteropoly acid, and its molecular formula is Na 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O.
Concrete synthetic route of the present invention is as follows:
A, PGEA is dissolved in the ultra-pure water, preparation obtains the polymer P GEA solution that the monomer unit concentration of electric charges is 0.01-0.1mol/L;
B, with ZnW 9Heteropoly acid is dissolved in the ultra-pure water, and preparation obtains the ZnW that unit charge concentration is 0.01-0.1mol/L 9Heteropoly acid solution, with the agitator vibration evenly;
C, with the polymer P GEA solution of step a preparation and the ZnW of step b preparation 9Heteropoly acid solution is by 1: 1-1: 1.1 volume ratio mixes, and obtains PGEA monomer unit concentration of electric charges and ZnW 9Heteropoly acid unit charge concentration ratio is 1: 1-10: 1 colloid solution, magnetic agitation 12-24 hour, be the daltonian bag filter of 3000-3800 dialysis 12-24 hour with molecular cut off, be 0.9-1.1Pa in vacuum, temperature is wrapped up ZnW for namely obtain PGEA under-65 ℃ to-55 ℃ the condition after lyophilizing on the freezer dryer 9The heteropoly acid nano-hybrid material.
The structural formula of described water-soluble polymer PGEA is shown below, wherein 50≤n≤80.
Figure BDA0000102873440000032
PGEA parcel ZnW with above-mentioned preparation 9The heteropoly acid nano-hybrid material is applied to suppress the growth of tumor cell.
Described PGEA parcel ZnW 9The heteropoly acid nano-hybrid material is applied to suppress the growth of tumor cell, and PGEA wraps up ZnW 9The working concentration of heteropoly acid nano-hybrid material is 0.125mg/mL-4mg/mL.
Described PGEA parcel ZnW 9The heteropoly acid nano-hybrid material is applied to suppress the growth of tumor cell, and tumor cell is mice glioma C6 cell line.
Beneficial effect of the present invention: by utilize between cationic polymer and the sandwich type heteropolyacid anions electrostatic interaction, with toxicity low-down water-soluble polymer cation PGEA and ZnW 9Heteropoly acid function anion is assembled in order by different proportion, obtains the nanoscale hydridization granule of big or small homogeneous, tactical rule.Through external MTT cytotoxicity test, find that the anti-tumor activity of hydridization granule obviously strengthens owing to the synergism between polymer and the polyacid.The present invention uses polymer cation PGEA with ZnW 9Heteropoly acid wraps up, and has realized ZnW 9The control of heteropoly acid discharges, and has studied its anti-tumor activity first, and test result shows PGEA parcel ZnW 9The heteropoly acid nano-hybrid material is a kind of potential antitumor drug.This method can be expanded on the one hand some potential applications of cationic polymer and electronegative polyoxoanion; On the other hand, this process has very strong practical significance for understanding the assembling chemical process.This hybrid material preparation process is simple, and environmental friendliness is workable, process economy and cleanliness without any pollution.
Description of drawings
Fig. 1. the PGEA parcel ZnW that embodiment 1 makes 9The Fourier transform infrared spectroscopy figure of heteropoly acid nano-hybrid material.
Fig. 2. the PGEA parcel ZnW that embodiment 1 makes 9The scanning electron microscope diagram of heteropoly acid nano-hybrid material.
Fig. 3. the inhibitory action for mice glioma C6 cell line growth reaches at 50% o'clock, polymer P GEA, heteropoly acid ZnW 9And the PGEA that embodiment 1 makes wraps up ZnW 9The concentration of heteropoly acid nano-hybrid material.
The specific embodiment
Embodiment 1
1, prepared polymer PGEA solution, the PGEA of weighing 101.5mg is dissolved in the ultra-pure water of 10ml, obtains the PGEA aqueous solution of 0.05mol/L unit charge concentration; The structural formula of PGEA is shown below, wherein 50≤n≤80;
2, preparation ZnW 9The aqueous solution of heteropoly acid, the Na of weighing 50.4mg 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2The O pressed powder is dissolved in the ultra-pure water of 10ml, obtains the ZnW that unit charge concentration is 0.01mol/L 9Heteropoly acid solution, with the agitator vibration evenly;
3,1: 1 by volume with ZnW 9Heteropoly acid solution dropwise adds in the polymer P GEA solution and mixes, and obtains PGEA unit charge concentration and ZnW 9Heteropoly acid unit charge concentration ratio is 5: 1 colloid solution, and magneton stirred 20 hours, is 3500 bag filter dialysis 12 hours with molecular weight, is 1Pa in vacuum, and temperature is wrapped up ZnW for namely obtain PGEA under-60 ℃ the condition after lyophilizing on the freezer dryer 9The heteropoly acid nano-hybrid material.
The PGEA parcel ZnW that obtains 9The heteropoly acid nano-hybrid material is the white solid powder; With 0.02mol/L concentration it is dispersed in formation colloidal state solution in the water, through scanning electron microscope and the test of laser particle size scatterometer, the pattern rule is consistent, and scanning electron microscope shows that the solid mean diameter is evenly distributed on 30-95nm; Its theoretical general formula is [M] +[WZn 3(H 2O) 2(ZnW 9O 34) 2/ 12] -, the monomer of M representation polymer PGEA wherein, its structure is shown below,
Figure BDA0000102873440000061
[WZn 3(H 2O) 2(ZnW 9O 34) 2] 12-Be ZnW 9The anion of heteropoly acid; ZnW 9Heteropoly acid is the sandwich type heteropoly acid, and its molecular formula is Na 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O.
With mtt assay test polymer PGEA, heteropoly acid ZnW 9With PGEA parcel ZnW 9The heteropoly acid nano-hybrid material (is designated as PGEA/ZnW 9) for the growth inhibited effect of the glioma C6 cell line of mice.The culture medium of using is Mi Libo (DMEM) high glucose medium, it contains 10% heat-inactivated fetal bovine serum, the penicillin of 100 unit/mL and the streptomycin sulfate of 100 mcg/ml, keep experiment condition to be simultaneously: 37 ℃, carbon dioxide content is 5% humid atmosphere.The glioma C6 cell line that will be in the mice of trophophase is spread the culture plate into 96 holes, keeps 10 4Cell/every plate, then contain DMEM 100 microlitres/the hole in cultivated 12 hours.Experimental group adds detected materials (polymer P GEA, the heteropoly acid ZnW of a series of different gradient concentrations (0.125mg/mL-4mg/mL) afterwards 9And PGEA/ZnW 9) fresh culture replace original culture medium, matched group adds the culture medium of not adding detected materials of equal volume, cultured cell is 12 hours respectively.Then, each hole drips MTT solution with PBS, adds 10 microlitres at every turn, reaches 0.5mg/mL up to the concentration of final MTT.Cultivate after 5 hours, careful sucking-off discards culture supernatant in the hole.The DMSO that adds 100 microlitres again to every hole vibrated 10 minutes, and the first a ceremonial jade-ladle, used in libation crystal that obtains is fully dissolved.Select the 570nm wavelength to measure the absorbance value in each hole and record the result in microplate reader.Utilize formula, cell survival rate=(experimental group absorbance value/do not contain the matched group absorbance value of test substance) * 100% converts resulting value to cell survival rate.Sample polymer PGEA, heteropoly acid ZnW 9And PGEA/ZnW 9The preparation of hybrid material gradient concentration: the preparation mother liquid concentration is 4mg/mL earlier, half-and-half dilute successively then and obtain a series of six concentration 4mg/mL, 2mg/mL, 1mg/mL, 0.5mg/mL, 0.25mg/mL, 0.125mg/mL, six groups of panel datas of each concentration determination, averaging at last is experimental result.Experimental result shows, PGEA/ZnW 9The IC of nano-hybrid material 50Value (certain density certain drug-induced apoptosis of tumor cells 50%, this concentration is called the half amount of suppression) is extremely low, and this shows that it has very strong anti-tumor activity, has the hybrid material of very high potential clinical medical value.
Embodiment 2
1, prepared polymer PGEA solution, the PGEA of weighing 40.6mg is dissolved in the ultra-pure water of 10ml, obtains the PGEA aqueous solution of 0.02mol/L unit charge concentration; The molecular formula of PGEA is shown below, wherein 55≤n≤60;
Figure BDA0000102873440000071
2, preparation ZnW 9Heteropoly acid solution is got the Na of 50.4mg 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2The O pressed powder is dissolved in the ultra-pure water of 10ml, obtains the ZnW that unit charge concentration is 0.01mol/L 9Heteropoly acid solution, with the agitator vibration evenly;
3,1: 1 by volume with ZnW 9Heteropoly acid solution dropwise adds in the polymer P GEA solution and mixes, and obtains PGEA unit charge concentration and ZnW 9Heteropoly acid unit charge concentration ratio is 2: 1 colloid solution, and magneton stirred 18 hours, is 3500 bag filter dialysis 13 hours with molecular weight, is 1Pa in vacuum, and temperature is wrapped up ZnW for namely obtain PGEA under-60 ℃ the condition after lyophilizing on the freezer dryer 9The heteropoly acid nano-hybrid material.
The PGEA parcel ZnW that obtains 9The heteropoly acid nano-hybrid material is the white solid powder; Concentration with 0.04mol/L is dispersed in formation colloidal state solution in the water with it, and through scanning electron microscope and the test of laser particle size scatterometer, the pattern rule is consistent, and mean diameter is evenly distributed on 40-80nm; Its theoretical general formula is [M] +[WZn 3(H 2O) 2(ZnW 9O 34) 2/ 12] -, the monomer of M representation polymer PGEA wherein, chemical formula is CH 3CH 2CCOOCH 2CHOHCH 2NH (CH 2) OH; [WZn 3(H 2O) 2(ZnW 9O 34) 2] 12-Be ZnW 9The anion of heteropoly acid; ZnW 9Heteropoly acid is the sandwich type heteropoly acid, and its molecular formula is Na 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O.
Embodiment 3
1, prepared polymer PGEA solution, the PGEA of weighing 20.3mg is dissolved in the ultra-pure water of 10ml, obtains the PGEA aqueous solution of 0.01mol/L unit charge concentration; The structural formula of PGEA is shown below, wherein 55≤n≤75;
Figure BDA0000102873440000081
2, preparation ZnW 9Heteropoly acid solution is got the Na of 50.4mg 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2The O pressed powder is dissolved in the ultra-pure water of 10ml, obtains the ZnW that unit charge concentration is 0.01mol/L 9Heteropoly acid solution, with the agitator vibration evenly;
3,1: 1 by volume with ZnW 9Heteropoly acid solution dropwise adds in the polymer P GEA solution and mixes, and obtains PGEA unit charge concentration and ZnW 9Heteropoly acid unit charge concentration ratio is 1: 1 colloid solution, and magneton stirred 24 hours, is 3500 bag filter dialysis 16 hours with molecular weight, is 1Pa in vacuum, and temperature is wrapped up ZnW for namely obtain PGEA under-60 ℃ the condition after lyophilizing on the freezer dryer 9The heteropoly acid nano-hybrid material.
The PGEA parcel ZnW that obtains 9The heteropoly acid nano-hybrid material is the white solid powder; Concentration with 0.06mol/L is dispersed in formation colloidal state solution in the water with it, and through scanning electron microscope and the test of laser particle size scatterometer, the pattern rule is consistent, and scanning electron microscope shows that the solid mean diameter is evenly distributed on 50-90nm; Its theoretical general formula is [M] +[WZn 3(H 2O) 2(ZnW 9O 34) 2/ 12] -, the monomer of M representation polymer PGEA wherein, chemical formula is CH 3CH 2CCOOCH 2CHOHCH 2NH (CH 2) OH; [WZn 3(H 2O) 2(ZnW 9O 34) 2] 12-Be ZnW 9The anion of heteropoly acid; ZnW 9Heteropoly acid is the sandwich type heteropoly acid, and its molecular formula is Na 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O.
Embodiment 4
1, prepared polymer PGEA solution, the PGEA of weighing 60.9mg is dissolved in the ultra-pure water of 5ml, obtains the PGEA aqueous solution of 0.06mol/L unit charge concentration; The structural formula of PGEA is shown below, wherein 60≤n≤75;
2, get the Na of 50.4mg 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2The O pressed powder is dissolved in the ultra-pure water of 10ml, obtains the ZnW that unit charge concentration is 0.01mol/L 9Heteropoly acid solution, with the agitator vibration evenly;
3,1: 1 by volume with ZnW 9Heteropoly acid solution dropwise adds in the polymer P GEA solution and mixes, and obtains PGEA unit charge concentration and ZnW 9Heteropoly acid unit charge concentration ratio is 1: 1 colloid solution, and magneton stirred 24 hours, is 3500 bag filter dialysis 18 hours with molecular weight, is 1Pa in vacuum, and temperature is wrapped up ZnW for namely obtain PGEA under-60 ℃ the condition after lyophilizing on the freezer dryer 9The heteropoly acid nano-hybrid material.
The PGEA parcel ZnW that obtains 9The heteropoly acid nano-hybrid material is the white solid powder; Concentration with 0.08mol/L is dispersed in formation colloidal state solution in the water with it, and through scanning electron microscope and the test of laser particle size scatterometer, the pattern rule is consistent, and scanning electron microscope shows that the mean diameter of solid is evenly distributed on 60-100nm; Its theoretical general formula is [M] +[WZn 3(H 2O) 2(ZnW 9O 34) 2/ 12] -, the monomer of M representation polymer PGEA wherein, chemical formula is CH 3CH 2CCOOCH 2CHOHCH 2NH (CH 2) OH; [WZn 3(H 2O) 2(ZnW 9O 34) 2] 12-Be ZnW 9The anion of heteropoly acid; ZnW 9Heteropoly acid is the sandwich type heteropoly acid, and its molecular formula is Na 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O.

Claims (5)

1. a polymer parcel heteropoly acid nano-hybrid material is characterized in that it is specially water-soluble polymer PGEA parcel ZnW 9The heteropoly acid nano-hybrid material; It is the white solid powder; Concentration range with 0.01mol/L-0.1mol/L is dispersed in formation colloidal state solution in the water with it, and through scanning electron microscope and the test of laser particle size scatterometer, the pattern rule is consistent, and scanning electron microscope shows that the solid mean diameter is evenly distributed on 30-100nm; The theoretical general formula of this nano-hybrid material is [M] +[WZn 3(H 2O) 2(ZnW 9O 34) 2/ 12] -, the monomer of M representation polymer PGEA wherein, its structure is shown below,
Figure FDA00002700193500011
[WZn 3(H 2O) 2(ZnW 9O 34) 2] 12-Be ZnW 9The anion of heteropoly acid; ZnW 9Heteropoly acid is the sandwich type heteropoly acid, and its molecular formula is Na 12[WZn 3(H 2O) 2(ZnW 9O 34) 2] 46H 2O;
The structural formula of described water-soluble polymer PGEA is shown below, wherein 50≤n≤80
Figure FDA00002700193500012
。
2. the preparation method of a kind of polymer parcel heteropoly acid nano-hybrid material as claimed in claim 1 is characterized in that its concrete synthetic route is as follows:
A, PGEA is dissolved in the ultra-pure water, preparation obtains the polymer P GEA solution that the monomer unit concentration of electric charges is 0.01-0.1mol/L;
B, with ZnW 9Heteropoly acid is dissolved in the ultra-pure water, and preparation obtains the ZnW that unit charge concentration is 0.01-0.1mol/L 9Heteropoly acid solution, with the agitator vibration evenly;
C, with the polymer P GEA solution of step a preparation and the ZnW of step b preparation 9Heteropoly acid solution mixes by the volume ratio of 1:1-1:1.1, obtains PGEA monomer unit concentration of electric charges and ZnW 9Heteropoly acid unit charge concentration ratio is the colloid solution of 1:1-10:1, magnetic agitation 12-24 hour, be the daltonian bag filter of 3000-3800 dialysis 12-24 hour with molecular cut off, be 0.9-1.1Pa in vacuum, temperature is wrapped up ZnW for namely obtain PGEA under-65 ℃ to-55 ℃ the condition after lyophilizing on the freezer dryer 9The heteropoly acid nano-hybrid material.
3. a kind of polymer parcel heteropoly acid nano-hybrid material as claimed in claim 1 is characterized in that, with the PGEA parcel ZnW of preparation 9The heteropoly acid nano-hybrid material is applied to suppress the growth of tumor cell.
4. a kind of polymer parcel heteropoly acid nano-hybrid material as claimed in claim 3 is characterized in that described PGEA parcel ZnW 9The heteropoly acid nano-hybrid material is applied to suppress the growth of tumor cell, and PGEA wraps up ZnW 9The working concentration of heteropoly acid nano-hybrid material is 0.125mg/mL-4mg/mL.
5. a kind of polymer parcel heteropoly acid nano-hybrid material as claimed in claim 3 is characterized in that described PGEA parcel ZnW 9The heteropoly acid nano-hybrid material is applied to suppress the growth of tumor cell, and tumor cell is mice glioma C6 cell line.
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