CN102258471A - 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, C.Burger, B.Chu such as light good harvest system and microreactor, 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 for environmental stimuli is when previous very popular research topic.People are by 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 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.), but the constructing of vesicle of the sharp response of thorniness that all has controlled response for multiple environmental stimuli still do not have report, and the sharp response of thorniness vesicle has the advantages such as multifunctionality that the single response vesicle does not possess.
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 by multiple weak reversible interactional synergism, so the supermolecule amphipathic nature material is the soft material that a class has good response 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 for the non-covalent interaction of representative has made in a large number, H.Xu, X.Zhang.Adv.Mater.2009,21,2849-2864.), but construct the also actually rare (Q.Yan of report of supermolecule amphipathic nature material by the host-guest inclusion coordination of macro ring subject and object, J.Yuan, Z.Cai, 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 carries out in the aqueous medium of bio-compatible 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, therefore 2045-2076.), have a wide range of applications in biotechnology and drug world by the constructed amphipathic nature material of itself and suitable object.
Calixarenes becomes the desirable molecule of constructing amphipathic nature material with its inherent bevel-type conformation and rigid framing structure.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 by calixarenes all is simultaneously to modify the synthetic method of covalent bond that hydrophilic group simultaneously modifies hydrophobic group by lower edge thereon 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 at 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 its medicine to load has high load factor; This supermolecule vesicle stimulations such as adding of temperature, oxidation-reduction 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 called for short C4AS based on sulfonation cup [4] aromatic hydrocarbons, is object with asymmetric purpurine, is called for short MVC
12, construct super-molecule assembling body, construction unit C4AS and MVC by host-guest inclusion coordination interaction
12Structure as follows:
It is characterized in that: described supermolecule vesicle preparation method is: with C4AS and MVC
12Being dissolved in the water also, uniform mixing can make supermolecule vesicle solution, described 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 described supermolecule vesicle solution generates once more along with the reduction of ambient temperature.
The depolymerization of supermolecule vesicle in the described supermolecule vesicle solution by adding cyclodextrin, described 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 described supermolecule vesicle solution is along with asymmetric purpurine unit MVC
12Single electron reduction and diminish, specific implementation method is: adding excessive hydrazine hydrate in supermolecule vesicle solution, 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 described supermolecule vesicle solution is along with asymmetric purpurine unit MVC
12Bielectron reduction and depolymerization, specific 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 described 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 preparation method is easy, and is main, object raw material consumption is few, to the load factor height of medicine; This supermolecule vesicle has thorniness and swashs response characteristic, and the stimulations such as adding of temperature, oxidation-reduction 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.
Fig. 6 for the thorniness in the assembling of 5 and 70 ℃ two temperature spot sulfonation cup [4] aromatic hydrocarbons and asymmetric purpurine supermolecule swash the response vesicle reciprocal alternating temperature ultraviolet spectra and cause the change curve of system 450nm wavelength place absorbance.
Fig. 7 is for adding the change curve that alpha-cyclodextrin causes system 450nm wavelength place 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 adding the change curve that beta-schardinger dextrin-causes system 450nm wavelength place 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 adding the change curve that gamma-cyclodextrin causes system 450nm wavelength place 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 of response vesicle, amycin and amycin load and the assembling of asymmetric purpurine supermolecule 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, described 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 by dynamic light scattering, transmission electron microscope and scanning electron microscope respectively, as 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 place absorbance, as shown in Figure 6, confirm that the generation of this supermolecule vesicle and depolymerization are along with the variation of ambient temperature can be back and forth.
2) in supermolecule vesicle solution, add cyclodextrin gradually, cause its variation, 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 at 450nm wavelength place absorbance; Transmission electron microscope image behind the adding alpha-cyclodextrin as shown in Figure 8, has confirmed the complete depolymerization of vesicle equally.In addition, the variation of 450nm wavelength place absorbance in the ultraviolet spectra experiment as 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 shows that the mean diameter of assembly in the system narrows down to original 1/3rd as shown in figure 11; The image of transmission electron microscope as shown in figure 12, confirms 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, as 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 as 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 as shown in figure 14, confirms vesicle depolymerization fully under this state.
Embodiment 3:
A kind of application of described 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 as follows:
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, described 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.
As 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, as 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, as 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 is discharged into cancerous cell from the supermolecule vesicle 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 (6)
1. nano-supermolecule vesicle preparation based on sulfonation cup [4] aromatic hydrocarbons, its construction unit is called for short C4AS based on sulfonation cup [4] aromatic hydrocarbons, is object with asymmetric purpurine, is called for short MVC
12, construct super-molecule assembling body, construction unit C4AS and MVC by host-guest inclusion coordination interaction
12Structure as follows:
It is characterized in that: described supermolecule vesicle preparation method is: with C4AS and MVC
12Being dissolved in the water also, uniform mixing can make supermolecule vesicle solution, described C4AS and MVC
12Concentration be respectively 0.04mM and 0.08mM.
2. according to the described nano-supermolecule vesicle preparation of claim 1 based on sulfonation cup [4] aromatic hydrocarbons, it is characterized in that: the depolymerization with the rising of ambient temperature in 5-70 ℃ of two temperature spot scopes of the supermolecule vesicle in the described supermolecule vesicle solution generates once more along with the reduction of ambient temperature.
3. according to the described nano-supermolecule vesicle preparation of claim 1 based on sulfonation cup [4] aromatic hydrocarbons, it is characterized in that: the depolymerization of the supermolecule vesicle in the described supermolecule vesicle solution by adding cyclodextrin, described cyclodextrin comprises alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin, and its concentration in supermolecule vesicle solution is respectively 0.16mM, 0.24mM and 0.24mM.
4. according to the described nano-supermolecule vesicle preparation based on sulfonation cup [4] aromatic hydrocarbons of claim 1, it is characterized in that: the supermolecule vesicle in the described supermolecule vesicle solution is along with asymmetric purpurine unit MVC
12Single electron reduction and diminish, specific implementation method is: adding excessive hydrazine hydrate in supermolecule vesicle solution, 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.
5. according to the described nano-supermolecule vesicle preparation based on sulfonation cup [4] aromatic hydrocarbons of claim 1, it is characterized in that: the supermolecule vesicle in the described supermolecule vesicle solution is along with asymmetric purpurine unit MVC
12Bielectron reduction and depolymerization, specific 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.
6. one kind according to claim 1 based on the application of 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.
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