CN110801520B - Preparation method of spirulina bioluminescence metal organic framework compound - Google Patents
Preparation method of spirulina bioluminescence metal organic framework compound Download PDFInfo
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- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0045—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent agent being a peptide or protein used for imaging or diagnosis in vivo
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Abstract
The invention discloses a preparation method of a spirulina bioluminescence metal organic framework compound, which comprises the steps of preparing a bioluminescence component and preparing a spirulina bioluminescence gamma-CD-MOFs solution, wherein the preparation method of the spirulina bioluminescence gamma-CD-MOFs solution comprises the steps of stirring and dissolving a mixed aqueous solution of gamma-cyclodextrin and a metal ligand until the mixed aqueous solution is clear, filtering to obtain a filtrate, adding the filtrate and the bioluminescence component into a small beaker in equal volume to obtain a mixed solution, then placing the small beaker in the center of a large beaker, injecting methanol or absolute ethyl alcohol into the large beaker, sealing the injected methanol or absolute ethyl alcohol with the liquid level higher than that of the mixed solution in the small beaker by using a freshness protection bag, and placing the beaker in a drying oven at room temperature or 60 ℃ for 2-7 days to obtain the spirulina bioluminescence metal organic framework compound. The obtained spirulina bioluminescence metal organic framework compound has blue and red fluorescence, is simple and convenient to operate, is non-toxic and can be produced in large quantities.
Description
Technical Field
The invention relates to a preparation method of a spirulina bioluminescence metal organic framework compound. It is prepared by introducing spirulina bioluminescence into MOFs hatching mother liquor and carrying out common solution crystallization. The prepared bioluminescent MOFs have a determined crystal structure, the maximum color development wavelength is 620nm, and strong blue fluorescence or red fluorescence is displayed.
Background
The rapid development of biological medicines is promoted by means of technologies such as fluorescence imaging, detection and treatment of sensors, and people hope to observe the growth of tumor cells and the reaction to medicines in vivo of living animals by means of technologies such as fluorescence labeling of polypeptides, small molecules and antibodies. The development of Metal-Organic Frameworks (MOFs) capable of being used for biomedical imaging has important significance for expanding the MOFs in biomedical drug loading and biological diagnosis.
The metal organic framework compounds, called MOFs for short, are a large class of organic-inorganic hybrid crystalline new materials. It has a large number of intramolecular voids and a periodic infinite network structure, and is generally formed by self-assembly between metal ions or metal clusters and organic ligands through coordination bonds. Since the crystalline material is discovered in 1989 that the function and structure can be effectively controlled, the crystalline material has larger specific surface area and porosity, and the crystalline material is rapidly developed in the field of coordination chemistry, at present, the crystalline material has been applied to a plurality of fields, such as adsorption, energy storage, catalysis, separation, drug loading, biosensing and the like.
Nevertheless, most of the MOFs are composed of synthetic organic substances and transition metals, so that the development of MOFs materials prepared by combining natural product source organic substances and metals with relatively low toxicity has important research significance in the biomedical field. The difficulty of preparing MOFs from natural products is that the construction units are asymmetric and are not beneficial to the crystallization formation of a porous frame. In 2010, Ronald A. Smoldone et al report that MOFs (gamma-CD-MOFs for short) prepared by taking gamma-cyclodextrin as a raw material opens a new way for constructing biocompatible MOFs materials.
The gamma-CD-MOFs are formed by coordinative bonding of a-OCCO-group on a D-glucopyranose unit in gamma-cyclodextrin with an alkali metal or alkaline earth metal cation of main group IA or IIA. Among them, the most easily produced CD-MOFs are KOH as the raw material, and the molecular formula of the formed CD-MOFs-1 is [ (C)48H80O40)(KOH)2]n. In 2012, Ross S.Forgan et al reported that groups arranged in the-OCCO-or-OCCN-arrangement had a high binding coefficient to alkali metals or alkaline earth metals, while in the D-glucopyranose units linked by alpha-1, 4 glycosidic linkages, there were groups arranged in the-OCCO-. Thus, the γ -CD-MOFs are expected to develop more in the biomedical field.
Reported studies of gamma-CD-MOFs have been mainly focused on size-nanosized, surface hydrophobization for better drug loading or to make them more stable when applied. Further functionalization of γ -CD-MOFs, such as improving biocompatibility and imparting bioluminescence properties, has not been reported.
Spirulina is one of the biomass materials which have recently been paid attention to in the medical field, and among them, spirulina, which is an important species, has been paid attention. The spirulina has four advantages: (1) the fiber content in the cell wall of the spirulina is very low, and the components in the cell are easy to extract, such as phycocyanin (promoting cell proliferation), spirulina polysaccharide, various pigments (inhibiting tumor cell growth) and the like; (2) the spirulina has low immunoreaction, can prevent foreign body rejection reaction generated when the tissue engineering scaffold is transplanted into a body, and can reduce inflammatory reaction caused by accumulation of lactic acid at an injured part; (3) the phycocyanin fluorescence efficacy in spirulina is 30 times of that of common fluorescein, the fluorescence quantum yield can reach 0.8, strong red fluorescence can be emitted after the phycocyanin fluorescence is excited by light, and the phycocyanin fluorescence can be used for near-infrared nondestructive living body imaging.
Based on the easy, simple and convenient preparation method of a large amount of spirulina bioluminescence gamma-CD-MOFs and the consideration of the biomedical activity of spirulina, the invention adopts a common solution method to prepare the blue or red fluorescence gamma-CD-MOFs, and the spirulina bioluminescence gamma-CD-MOFs is subjected to crystal structure characterization and fluorescence analysis, thereby determining the effect of the invention.
Disclosure of Invention
The invention aims to provide a preparation method of a spirulina bioluminescence metal organic framework compound, and the obtained spirulina bioluminescence gamma-CD-MOFs has determined complete three-dimensional morphology, crystal structure and fluorescence characteristic.
The invention provides a preparation method of a spirulina bioluminescence metal organic framework compound, which comprises the following steps:
(1) preparation of bioluminescent component: the biological fluorescent component comprises one of spirulina suspension, spirulina supernatant and phycocyanin aqueous solution; drying, crushing and sieving spirulina to obtain spirulina powder, mixing the spirulina powder and deionized water to prepare a 5-10 g/L spirulina aqueous solution, magnetically stirring for 4-8 h at room temperature-40 ℃ to obtain a spirulina suspension, further performing centrifugal separation on the spirulina suspension at 3000rpm/min for 30min to obtain a spirulina supernatant, and preparing phycocyanin into a 0.5-1.0 g/L aqueous solution by using deionized water to obtain a phycocyanin aqueous solution;
(2) preparing a spirulina bioluminescence gamma-CD-MOFs solution: stirring and dissolving a mixed aqueous solution of gamma-cyclodextrin and a metal ligand until the mixed aqueous solution is clear, filtering to obtain a filtrate, adding the filtrate and the bioluminescent component obtained in the step (1) into a small beaker in equal volume to obtain a mixed solution, then placing the small beaker containing the mixed solution into a central position of a large beaker, injecting methanol or absolute ethyl alcohol into the large beaker, sealing the large beaker by using a freshness protection package, and placing the large beaker in a drying oven at room temperature or 60 ℃ for 2-7 days to obtain the spirulina bioluminescent metal organic framework compound; wherein, in the mixed water solution of the gamma-cyclodextrin and the metal ligand, the concentration of the gamma-cyclodextrin is 130g/L, and the concentration of the metal ligand is 45 g/L.
In the step (1), the vacuum drying temperature of the spirulina is between room temperature and 40 ℃, and the drying time is 12 hours.
In the step (1), the sieving is 100-mesh sieving.
In the step (2), the metal ligand is one of sodium chloride, potassium hydroxide and rubidium hydroxide.
In the invention, the co-crystallization time is 2-7 days, so that the growth time is long when the generation of precipitation in the solution or the appearance of crystals on the bottle wall can be observed by naked eyes.
According to the process conditions, the obtained spirulina supernatant participates in the preparation of bioluminescence gamma-CD-MOFs which shows blue fluorescence; the biological fluorescence gamma-CD-MOFs which participates in the preparation of the spirulina suspension shows red fluorescence, and both the two have determined crystal structures.
The invention is characterized in that: the spirulina biological medicine is mainly used for improving the cell proliferation capacity and the tissue repair speed, resisting bacteria or assisting treatment and the like. However, the inventor finds that the spirulina supernatant, the spirulina suspension and the phycocyanin aqueous solution are introduced into the gamma-CD-MOFs hatching mother liquor for cocrystallization, the obtained gamma-CD-MOFs still has a complete crystal structure, the bioluminescence of the spirulina or the phycocyanin in the crystallization mother liquor can be still maintained, and the gamma-CD-MOFs fluorescent characteristic and biocompatibility are endowed. The gamma-CD-MOFs have better biocompatibility and fluorescence function, and are expected to be used for diagnosis and treatment integration of the gamma-CD-MOFs.
The invention has the beneficial effects that: the spirulina or phycocyanin has biological curative effect and fluorescence effect, and the research of sensors and implantable biological fluorescent MOFs which take the spirulina or phycocyanin as biological fluorescence is still in the blank field. The invention advances the development of the research of the gamma-CD-MOFs with integrated diagnosis and treatment and controlled drug release development. In particular to (1) the preparation of bioluminescent MOFs by compounding spirulina or phycocyanin with the MOFs is reported for the first time in the reference range of literature; (2) the MOFs obtained by taking spirulina supernatant as a functional component shows blue fluorescence is reported for the first time; (3) the fluorescence intensity of the bioluminescent MOFs obtained by using spirulina or phycocyanin as a bioluminescent component is enhanced; (4) the spirulina is a natural material, has biological effects of antibiosis, antiphlogosis, near-infrared response auxiliary treatment and the like, and the prepared product is expected to be applied in diagnosis and treatment integration; (5) the product is loaded in a film or block material, and can realize the instant fluorescent display function.
Drawings
FIG. 1 is a UV fluorescence chart of example 1 of the present invention.
FIG. 2 is a graph of UV fluorescence of example 5 in the present invention.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Preparation of bioluminescent component: the biological fluorescent component is spirulina suspension or spirulina supernatant; vacuum drying Spirulina at 40 deg.C for 12 hr, pulverizing, sieving with 100 mesh sieve to obtain Spirulina powder, mixing with deionized water to obtain 7g/L Spirulina water solution, magnetically stirring at room temperature for 6 hr to obtain Spirulina suspension, and centrifuging at 3000rpm/min for 30min to obtain Spirulina supernatant.
Preparing a spirulina bioluminescence gamma-CD-MOFs solution: stirring and dissolving a mixed aqueous solution of gamma-cyclodextrin and a metal ligand until the mixed aqueous solution is clear, wherein the concentration of the gamma-cyclodextrin in the mixed aqueous solution is 130g/L, the concentration of the metal ligand is 45g/L, filtering to obtain a filtrate, adding 10ml of the filtrate into a small beaker, adding 10ml of a bioluminescent component into the small beaker to obtain a mixed solution, then placing the small beaker containing the mixed solution in the central position of a large beaker, injecting the mixed solution into the large beaker, wherein the liquid level of the injected methanol is 2mm higher than that of the mixed solution in the small beaker, at the moment, using 50ml of methanol, sealing the mixed solution by using a freshness protection bag, placing the mixed solution in an oven at room temperature or 60 ℃ for 2-7 days, and collecting a sample.
The compositions and effects of examples 1 to 10 are shown in Table 1, and examples 1 to 10 were performed according to the above-described processes except that different bioluminescent components, metal ligands and incubation temperatures were used.
Table 1:
FIG. 1 (1) shows Spirulina supernatant, which is prepared by co-crystallizing with hatching mother liquor to obtain γ -CD-MOFs (2), i.e. example 1 shows stronger blue fluorescence characteristics; in FIG. 2, (3) and (4) show strong red fluorescence for the γ -CD-MOFs obtained by co-crystallization of the suspension and the mother liquor. The differences and variations of the γ -CD-MOFs of example 1 and example 5 are quite apparent.
When the incubation temperature was changed, as seen from examples 1 and 9, and examples 5 and 10, the growth time of the crystals decreased greatly with the increase in temperature, from 7 days to 2 days.
When the metal ligand is changed, see examples 1-4 and examples 5-8, bioluminescent gamma-CD-MOFs with uniform size and shape can be obtained.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications and substitutions may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (4)
1. A preparation method of a spirulina bioluminescence metal organic framework compound is characterized by comprising the following steps:
(1) preparation of bioluminescent component: the biological fluorescent component is one of spirulina suspension and spirulina supernatant; the preparation method comprises the steps of carrying out vacuum drying, crushing and sieving on spirulina to obtain spirulina powder, mixing the spirulina powder and deionized water to prepare a spirulina aqueous solution with the concentration of 5-10 g/L, carrying out magnetic stirring for 4-8 hours at the room temperature-40 ℃ to obtain a spirulina suspension, and further carrying out centrifugal separation on the spirulina suspension at 3000rpm/min for 30 minutes to obtain a spirulina supernatant;
(2) preparing a spirulina bioluminescence gamma-CD-MOFs solution: stirring and dissolving a mixed aqueous solution of gamma-cyclodextrin and a metal ligand until the mixed aqueous solution is clear, filtering to obtain a filtrate, adding the filtrate and the bioluminescent component obtained in the step (1) into a small beaker in equal volume to obtain a mixed solution, then placing the small beaker containing the mixed solution into a central position of a large beaker, injecting methanol or absolute ethyl alcohol into the large beaker, sealing the large beaker by using a freshness protection package, and placing the large beaker in a drying oven at room temperature or 60 ℃ for 2-7 days to obtain the spirulina bioluminescent metal organic framework compound; wherein, in the mixed water solution of the gamma-cyclodextrin and the metal ligand, the concentration of the gamma-cyclodextrin is 130g/L, and the concentration of the metal ligand is 45 g/L.
2. The method for preparing a spirulina bioluminescent metal organic framework compound according to claim 1, wherein the spirulina is vacuum dried at room temperature to 40 ℃ for 12 hours in step (1).
3. The method for preparing a spirulina bioluminescent metal organic framework compound according to claim 1, wherein in the step (1), the sieving is performed by a 100-mesh sieve.
4. The method for preparing a spirulina bioluminescent metal organic framework compound according to claim 1, wherein in step (2), the metal ligand is one of sodium chloride, potassium hydroxide and rubidium hydroxide.
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