CN102258471B - Preparation and application of sulfonated calix [4] arene-based nano supramolecular vesicles - Google Patents
Preparation and application of sulfonated calix [4] arene-based nano supramolecular vesicles Download PDFInfo
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Abstract
The invention relates to preparation of sulfonated calix [4] arene-based nano supramolecular vesicles. According to the construction unit, sulfonated calix [4] arene is used as a subject (C4AS), asymmetrical purpurine is used as an object (MVC12), and a supramolecular assembly is constructed by including and coordinating interaction of the subject and the object. The preparation method comprises the following steps of: dissolving the C4AS and the MVC12 into water, and uniformly mixing the C4AS and the MVC12. The invention has the advantages that: the preparation method is simple and convenient; the consumption of raw materials of the subject and the object is low, and the subject and the object have high medicament load rate; the supramolecular vesicles have good response to the stimulus of external temperature, oxidation and reduction, addition of cyclodextrin and the like in short time; the supramolecular vesicles can load hydrophilic anti-cancer adriamycin; compared with pure adriamycin, the killing effect of the loaded adriamycin on cancer cells is not changed, and the toxic effect of the loaded adriamycin on normal cells is obviously reduced; and the supramolecular vesicles have broad application prospect in the fields of load, transport and targeted release of anti-cancer medicaments.
Description
[technical field]
The invention belongs to nano-supermolecule material technology field, particularly a kind of preparation of nano-supermolecule vesicle and application based on sulfonation cup [4] aromatic hydrocarbons.
[background technology]
Vesicle is the important building block of life entity, has important and application widely at chemistry, biology and material science, and for example: medicine/gene transmits system, (S.Zhou such as light good harvest system and microreactor; C.Burger, B.Chu, M.Sawamura, N.Nagahama; M.Toganoh, U.E.Hackler, H.Isobe; E.Nakamura.Science 2001,291,1944-1947; (2) D.E.Discher, A.Eisenberg.Science2002,297,967-973; (3) X.Zhang, S.Rehm, M.M.Safont-Sempere, F.W ü rthner.Nat.Chem.2009,1,623-629.).The controlled regulation and control of vesicle assembly gathering/depolymerization realize often these functions precondition (X.Guo, F.C.Szoka.Acc.Chem.Res.2003,36,335-341.).Therefore, constructing the vesicle that has a good response property for environmental stimuli is when the popular research topic of previous ten minutes.People are through making great efforts to have constructed vesicle (M.Lee, S.-J.Lee, L.-H.Jiang.J.Am.Chem.Soc.2004,126, the 12724-12725 that has single response property for stimulations such as ambient light, electricity, heat and pH in recent years; (2) C.Wang, Q.Chen, H.Xu, Z.Wang, X.Zhang.Adv.Mater.2010,22,2553-2555; (3) A.Napoli, M.Valentini, N.Tirelli, M.M ü ller, J.A.Hubbell.Nat.Mater.2004,3,183-189; (4) E.Kim, D.Kim, H.Jung, J.Lee; S.Paul, N.Selvapalam, Y.Yang, N.Lim; C.G.Park, K.Kim.Angew.Chem., Int.Ed.2010,49; 4405-4408.), does not still have report but swash constructing of vesicle of response, and the sharp vesicle that responds of thorniness has the advantages such as multifunctionality that single response property vesicle does not possess for the thorniness that multiple environmental stimuli all has a controlled response.
The supermolecule means are methods that the another kind except that the covalent bond means is constructed amphipathic assembly.Because the amphipathic assembly of constructing with the supermolecule means is to form through multiple weak reversible interactional synergism, so the supermolecule amphipathic nature material is one type of soft material with good response property and Modulatory character.Up to the present, with hydrogen bond, charge transfer and π ... π interacts to wait and is used for constructing the supermolecule amphipathic nature material and shows good performance (Y.Wang, H.Xu for the non-covalent interaction of representative has made in a large number; X.Zhang.Adv.Mater.2009,21,2849-2864.); But construct report also actually rare (Q.Yan, J.Yuan, the Z.Cai of supermolecule amphipathic nature material through the host-guest inclusion coordination of macro ring subject and object; Y.Xin, Y.Kang, Y.Yin.J.Am.Chem.Soc.2010; 132,9268-9270; (2) Y.J.Jeon, P.K.Bharadwaj, S.W Choi, J.W Lee, K.Kim.Angew.Chem.Int.Ed.2002,41,4474-4476.).Be that the inclusion coordination of the macro ring subject and object molecule of representative interacts and normally in the aqueous medium of bio-compatible, carries out with cyclodextrin, sulfonation calixarenes and calabash urea etc., and this medium is not very favourable for other non-covalent interaction.Because these macro ring main bodys have been proved to be molecule (F.Perret, A.N.Lazar, A.W Coleman.Chem.Commun.2006, the 2425-2438 of bio-compatible equally; (2) K.Wang, D.-S.Guo, H.-Q.Zhang, D.Li, X.-L.Zheng, Y.Liu.J.Med.Chem.2009,52,6402-6412; (3) V.D.Uzunova, C.Cullinane, K.Brix, W M.Nau, A.I.Day.Org.Biomol.Chem.2010,8,2037-2042; (4) K.Uekama, F.Hirayama, T.Irie.Chem.Rev.1998,98,2045-2076.), therefore have a wide range of applications in biotechnology and drug world through itself and the constructed amphipathic nature material of suitable object.
Calixarenes becomes the desirable molecule of constructing amphipathic nature material with its inherent bevel-type conformation and the framing structure that ossifys.The bevel-type conformation of calixarenes is to form the accumulative prerequisite of amphipathic nature material higher curvature; The framing structure that calixarenes ossifys can improve the stability of amphipathic collective.But up to the present except two nearest utilize calixarenes cavity and object inclusion coordination construct the report of amphipathic collective (K.Wang, D.-S.Guo, Y.Liu.Chem.Eur, J.2010,16,8006-8011; (2) V.Francisco, N.Basilio, L.Garc í a-R í o; J.R.Leis; E.F.Maques, C.V á zquez-V á zquez.Chem.Commun.2010,46; 6551-6553.), other report of constructing vesicle through calixarenes all is simultaneously to modify the synthetic method of covalent bond that hydrophilic group simultaneously modifies hydrophobic group through lower edge above that to obtain.
At present; Utilize cancer therapy drug the cancer patient to be carried out cancer therapy drug also has very big toxic action to the human normal cell in the therapeutic process when killing and wounding cancerous cell, the nano carrier material that therefore prepares bio-compatible carries out load, transportation and targeting to anticarcinogen and discharges with this and reduce anticarcinogen for Normocellular toxic action or improve anticarcinogen the fragmentation effect of cancerous cell is had huge actual application value in daily life.
[summary of the invention]
The objective of the invention is to above-mentioned technical Analysis; A kind of preparation of nano-supermolecule vesicle and application based on sulfonation cup [4] aromatic hydrocarbons is provided; The response vesicle swashs based on the thorniness of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine binary supermolecule in this supermolecule vesicle system; The existence of sulfonation cup [4] aromatic hydrocarbons can induce the critical aggregate concentration of asymmetric purpurine to descend about 1000 times; Thereby it is very low to form employed two component concentrations of this supermolecule vesicle, so it has high load factor to loaded drugs; This supermolecule vesicle stimulations such as adding of temperature, OR and cyclodextrin to external world has good response; This supermolecule vesicle can the hydrophilic anticarcinogen amycin of load in addition; Amycin after the load does not change than simple amycin the lethal effect of cancerous cell, and it significantly decreases than simple amycin to Normocellular toxic action.
Technical scheme of the present invention:
A kind of nano-supermolecule vesicle preparation based on sulfonation cup [4] aromatic hydrocarbons, its construction unit is the main body with sulfonation cup [4] aromatic hydrocarbons, is called for short C4AS, is object with asymmetric purpurine, is called for short MVC
12, construct super-molecule assembling body, construction unit C4AS and MVC through host-guest inclusion coordination interaction
12Structure following:
It is characterized in that: said supermolecule vesicle method for preparing is: with C4AS and MVC
12Being dissolved in the water also, uniform mixing can make supermolecule vesicle solution, said C4AS and MVC
12Concentration be respectively 0.04mM and 0.08mM.
The depolymerization with the rising of ambient temperature in 5-70 ℃ of two temperature spot scopes of supermolecule vesicle in the said supermolecule vesicle solution generates along with the reduction of ambient temperature once more.
The depolymerization of supermolecule vesicle in the said supermolecule vesicle solution through adding cyclodextrin, said cyclodextrin comprises alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin, its concentration in supermolecule vesicle solution is respectively 0.16mM, 0.24mM and 0.24mM.
Supermolecule vesicle in the said supermolecule vesicle solution is along with asymmetric purpurine unit MVC
12Single electron reduction and diminish; The practical implementation method is: in supermolecule vesicle solution, adding excessive hydrazine hydrate, to make asymmetric purpurine unit revert to the radical cation state be the single electron reduction, and the mean diameter of supermolecule vesicle narrows down to original 1/3rd.
Supermolecule vesicle in the said supermolecule vesicle solution is along with asymmetric purpurine unit MVC
12Bielectron reduction and depolymerization, the practical implementation method is: the reduction potential of 1.6V is acted in the supermolecule vesicle solution asymmetric purpurine unit MVC after 30 minutes
12To revert to the electric neutrality state, i.e. bielectron reduction, and make the complete depolymerization of supermolecule vesicle.
A kind of application of said nano-supermolecule vesicle based on sulfonation cup [4] aromatic hydrocarbons loads to hydrophilic anticarcinogen amycin in the cavity of supermolecule vesicle.
Advantage of the present invention is: the nano-supermolecule vesicle that assembling is constructed based on sulfonation cup [4] aromatic hydrocarbons and asymmetric purpurine binary supermolecule, and method for preparing is easy, and is main, object raw material consumption is few, and is high to the load factor of medicine; This supermolecule vesicle has thorniness and swashs response characteristic, and the stimulations such as adding of temperature, OR and cyclodextrin just have good response at short notice to external world; This supermolecule vesicle can the hydrophilic anticarcinogen amycin of load and load after amycin the lethal effect of cancerous cell is not changed than simple amycin; And it significantly decreases than simple amycin to Normocellular toxic action, and it has broad application prospects in cancer therapy drug load, transportation and targeting release field.
[description of drawings]
There is the critical aggregate concentration figure of asymmetric purpurine down in Fig. 1 for sulfonation cup [4] aromatic hydrocarbons.
Fig. 2 swashs the dynamic light scattering figure of response vesicle for the thorniness of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule.
Fig. 3 swashs the transmission electron microscope image of response vesicle for the thorniness of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule.
Fig. 4 swashs the scanning electron microscope image of response vesicle for the thorniness of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule.
Fig. 5 swashs the variation relation figure of the light scattering intensity of response vesicle with temperature and time for the thorniness of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule.
The reciprocal alternating temperature ultraviolet spectra that Fig. 6 responds vesicle for the thorniness in the assembling of 5 and 70 ℃ two temperature spot sulfonation cup [4] aromatic hydrocarbons and asymmetric purpurine supermolecule swashs and cause the change curve of system 450nm wavelength absorbance.
Fig. 7 is for add the change curve that alpha-cyclodextrin causes system 450nm wavelength absorbance gradually in the supermolecule vesicle system of sulfonation cup [4] aromatic hydrocarbons of constructing and the assembling of asymmetric purpurine.
The transmission electron microscope image of Fig. 8 after for adding alpha-cyclodextrin in the supermolecule vesicle system of sulfonation cup [4] aromatic hydrocarbons of constructing and asymmetric purpurine assembling.
Fig. 9 is for add the change curve that beta-schardinger dextrin-causes system 450nm wavelength absorbance gradually in the supermolecule vesicle system of sulfonation cup [4] aromatic hydrocarbons of constructing and the assembling of asymmetric purpurine.
Figure 10 is for add the change curve that gamma-cyclodextrin causes system 450nm wavelength absorbance gradually in the supermolecule vesicle system of sulfonation cup [4] aromatic hydrocarbons of constructing and the assembling of asymmetric purpurine.
Figure 11 is the thorniness sharp response vesicle of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule and the dynamic light scattering comparison diagram that asymmetric purpurine unit is reduced the back and reoxidizes by the excess hydrazine hydrate single electron thereof.
Figure 12 swashs the transmission electron microscope image of response vesicle after its asymmetric purpurine unit is by the reduction of excess hydrazine hydrate single electron for the thorniness of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule.
Figure 13 is the cyclic voltammetry experiment curve of the supermolecule vesicle system of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine.
Figure 14 for the supermolecule vesicle of sulfonation cup [4] aromatic hydrocarbons and asymmetric purpurine assembling in effect under reduction potential (reference is in the Ag/AgCl electrode) condition of 1.6V after 30 minutes, asymmetric purpurine unit is the transmission electron microscope image during to the electric neutrality state by electrochemical reduction.
Figure 15 is that sulfonation cup [4] aromatic hydrocarbons of amycin load and the thorniness of asymmetric purpurine supermolecule assembling swash the ultra-violet absorption spectrum variation diagram that responds vesicle.
The thorniness that Figure 16 swashs sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine supermolecule of response vesicle, amycin and amycin load for the thorniness of sulfonation cup [4] aromatic hydrocarbons of load amycin not and the assembling of asymmetric purpurine supermolecule swashs the response vesicle and hatches four days the quantity comparison diagram of respectively organizing cell of back continuous record with NIH3T3 cell (normal cell) respectively.
Figure 17 is hatched four days the quantity comparison diagram of respectively organizing cell of back continuous record with HepG-2 cell (cancerous cell) respectively for the amycin that amycin and the thorniness that is sulfonated the assembling of cup [4] aromatic hydrocarbons and asymmetric purpurine supermolecule swash after the load of response vesicle.
Figure 18 is hatched form and the amycin of living cells after 96 hours with NIH3T3 cell (normal cell) respectively and is sulfonated cup [4] aromatic hydrocarbons and the thorniness of asymmetric purpurine supermolecule assembling swashs the amycin that responds after the vesicle load is hatched the form of living cells after 96 hours respectively with HepG-2 cell (cancerous cell) comparison diagram for the thorniness of sulfonation cup [4] aromatic hydrocarbons of amycin and amycin load and the assembling of asymmetric purpurine supermolecule swashs the response vesicle.
[specific embodiment]
Embodiment 1:
A kind of nano-supermolecule vesicle preparation based on sulfonation cup [4] aromatic hydrocarbons is with C4AS and MVC
12Being dissolved in the water also, uniform mixing can make supermolecule vesicle solution, said C4AS and MVC
12Concentration be respectively 0.04mM and 0.08mM.
There is not MVC in the presence of the C4AS
12Critical aggregate concentration be 2 * 10
-2M (M.Krieg, M.-P.Pileni, A.M.Braun, M.Gratzel.J.Colloid Interface Sci.1981,83,209-213.); As shown in Figure 1, the existence of sulfonation cup [4] aromatic hydrocarbons can induce the critical aggregate concentration of asymmetric purpurine to descend about 1000 times.
The particle diameter of this supermolecule vesicle and pattern characterize through dynamic light scattering, transmission electron microscope and scanning electron microscope respectively, like Fig. 2, Fig. 3, shown in Figure 4.
Embodiment 2:
The thorniness of this supermolecule vesicle swashs the experimental verification of response:
1) supermolecule vesicle solution is warming up to 70 ℃ from 15 ℃; As shown in Figure 5; Its light scattering intensity drops to the light scattering intensity of water at last along with tangible decline takes place at short notice in the rising of temperature, shows the rising completely depolymerization of constructed supermolecule vesicle along with ambient temperature.In addition, the reciprocal alternating temperature ultraviolet experiment of 5 and 70 ℃ of two temperature spots and cause the variation of system 450nm wavelength absorbance, as shown in Figure 6, the generation and the depolymerization that confirm this supermolecule vesicle are along with the variation of ambient temperature can be back and forth.
2) in supermolecule vesicle solution, add cyclodextrin gradually, cause its variation at 450nm wavelength absorbance, as shown in Figure 7, show that the alpha-cyclodextrin (0.16mM) that adds the asymmetric purpurine amount of twice can make the complete depolymerization of vesicle; Transmission electron microscope image behind the adding alpha-cyclodextrin, as shown in Figure 8, confirmed the complete depolymerization of vesicle equally.In addition, the variation of 450nm wavelength absorbance in the ultraviolet spectra experiment like Fig. 9, shown in Figure 10, confirms that the beta-schardinger dextrin-(0.24mM) or the gamma-cyclodextrin (0.24mM) that add three times of asymmetric purpurine amounts can make the complete depolymerization of vesicle equally.
3) in supermolecule vesicle solution, add excessive hydrazine hydrate; Make asymmetric purpurine unit revert to radical cation state (single electron reduction); The result of dynamic light scattering is shown in figure 11, shows that the mean diameter of assembly in the system narrows down to original 1/3rd; The image of transmission electron microscope, shown in figure 12, confirm that the pattern of these assemblies remains the vesicle structure.With the dynamic light scattering result of asymmetric purpurine unit reoxidation behind two positive charge states, shown in figure 11, show that the particle diameter of vesicle can return to original size again.
4) supermolecule vesicle solution is carried out cyclic voltammetry experiment; Experimental result is shown in figure 13; According to this result the reduction potential (reference is in the Ag/AgCl electrode) of 1.6V is acted in the supermolecule vesicle system of sulfonation cup [4] aromatic hydrocarbons and the assembling of asymmetric purpurine, asymmetric purpurine unit will revert to electric neutrality state (bielectron reduction) after 30 minutes; The image of transmission electron microscope, shown in figure 14, confirm vesicle depolymerization fully under this state.
Embodiment 3:
A kind of application of said nano-supermolecule vesicle based on sulfonation cup [4] aromatic hydrocarbons loads to hydrophilic anticarcinogen amycin in the cavity of supermolecule vesicle of preparation, and method is following:
1) with amycin, C4AS and MVC
12The back mix homogeneously that is dissolved in the water obtains solution; Under 10000 rev/mins of conditions centrifugal 2 minutes; Dialysing does not then observe the fluorescence of amycin in the solution outside bag filter, can make the supermolecule vesicle of amycin load, said amycin, C4AS and MVC
12Concentration be respectively 0.01mM, 0.04mM and 0.08mM.Detection shows: the supermolecule vesicle is respectively 86.0% and 6.1% to the envelop rate and the load factor of amycin.
Shown in figure 15, the supermolecule vesicle is confirmed by the ultra-violet absorption spectrum variation the successful load of amycin.
2) the supermolecule vesicle of supermolecule vesicle, amycin and the amycin load of load amycin is not hatched with NIH3T3 cell (normal cell) respectively; Continuous record was respectively organized the quantity of cell in four days; Shown in figure 16; The result shows that the cytotoxicity of the supermolecule vesicle of load amycin is not well below the cytotoxicity of anticarcinogen amycin; And by the amycin of supermolecule vesicle load Normocellular toxic action is also significantly decreased than simple amycin.
3) the supermolecule vesicle of amycin and amycin load is hatched with HepG-2 cell (cancerous cell) respectively; Continuous record was respectively organized the quantity of cell in four days; Shown in figure 17; The result shows, is not changed than simple amycin by the lethal effect of the amycin of supermolecule vesicle load to cancerous cell.This is that normal cell is higher to be caused than being discharged into because the interaction of anticarcinogen amycin and cancerous cell, causes its efficient that from the supermolecule vesicle, is discharged into cancerous cell than stronger with normal cell.
Figure 18 is hatched form and the amycin of living cells after 96 hours with NIH3T3 cell (normal cell) respectively and is sulfonated cup [4] aromatic hydrocarbons and the thorniness of asymmetric purpurine supermolecule assembling swashs the amycin that responds after the vesicle load is hatched the form of living cells after 96 hours respectively with HepG-2 cell (cancerous cell) comparison diagram for the thorniness of sulfonation cup [4] aromatic hydrocarbons of amycin and amycin load and the assembling of asymmetric purpurine supermolecule swashs the response vesicle.
Claims (1)
1. application based on the nano-supermolecule vesicle of sulfonation cup [4] aromatic hydrocarbons; It is characterized in that: hydrophilic anticarcinogen amycin is loaded in the cavity of supermolecule vesicle of preparation, method is following: amycin, sulfonation cup [4] aromatic hydrocarbons are called for short C4AS and asymmetric purpurine is called for short MVC
12The back mix homogeneously that is dissolved in the water obtains solution; Under 10000 rev/mins of conditions centrifugal 2 minutes; Dialysing does not then observe the fluorescence of amycin in the solution outside bag filter, can make the supermolecule vesicle of amycin load, said amycin, C4AS and MVC
12Concentration be respectively 0.01 mM, 0.04 mM and 0.08 mM.
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| CN104473902B (en) * | 2014-11-21 | 2017-03-22 | 南开大学 | Light and thermal controlled nano supermolecule vesicle as well as preparation method and application thereof |
| CN105130882A (en) * | 2015-07-15 | 2015-12-09 | 天津师范大学 | Construction of sulfonated calyx[4]arene-methyl-naphthyl-viologen simulative biologic region selective recognition bionic system |
| CN105566129B (en) * | 2015-12-22 | 2017-09-12 | 南开大学 | A kind of amphiphilic calixarenes AmC5A nano supermolecule assembly and its preparation method and application |
| CN108467489A (en) * | 2018-03-09 | 2018-08-31 | 南京信息工程大学 | A kind of cucurbit(7)uril and sulfonation cup [4] aryl supermolecule polymer and preparation method and application |
| CN108435099B (en) * | 2018-03-13 | 2020-02-07 | 天津师范大学 | Supramolecular Gemini surfactant based on calix pyridine and preparation method and application thereof |
| CN108435100B (en) * | 2018-03-13 | 2020-01-07 | 天津师范大学 | Preparation method for improving use efficiency of anionic Gemini surfactant |
| CN114848839A (en) * | 2021-02-03 | 2022-08-05 | 苏州隽德生物科技有限公司 | Azocalixarene pharmaceutic adjuvant and application thereof |
| CN115745757B (en) * | 2022-11-07 | 2024-04-26 | 中国人民解放军军事科学院军事医学研究院 | Synthesis of liquid-state polyglycol column arene derivative and application of liquid-state polyglycol column arene derivative in transdermal pharmacodynamic molecule slow release |
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