CN104759242B - A kind of method utilizing yeast synthesis metallic organic framework hollow structure capsule - Google Patents
A kind of method utilizing yeast synthesis metallic organic framework hollow structure capsule Download PDFInfo
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- CN104759242B CN104759242B CN201510147358.1A CN201510147358A CN104759242B CN 104759242 B CN104759242 B CN 104759242B CN 201510147358 A CN201510147358 A CN 201510147358A CN 104759242 B CN104759242 B CN 104759242B
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Abstract
The invention discloses a kind of method utilizing yeast synthesis metallic organic framework hollow structure capsule, described method is: slaine or organic ligand are made an addition in cell wall suspension, 50 140 DEG C of stirring 6 24h, it is thus achieved that the cell wall containing metal ion or the cell wall containing organic ligand；Being scattered in organic ligand saline solution by cell wall containing metal ion, or be scattered in metal salt solution by the cell wall containing organic ligand, 50 140 DEG C are slowly stirred crystallization, i.e. obtain metallic organic framework cell wall capsule；The structure of the metallic organic framework cell wall capsule synthesized by the present invention can be controlled according to the condition of synthesis and process, a size of tens nanometer is to hundreds of nanometers, can be to be grown in cell wall inner surface and outer surface by controlling to soak the sequential control metallic organic framework layer of part and metal salt solution, the metallic organic framework cell wall capsule of synthesis has good solvent resistance and good mechanical strength.
Description
(1) technical field
The present invention relates to the preparation of a kind of metallic organic framework, be a supporting particularly to utilizing yeast
Become the synthetic method of metallic organic framework-cell wall capsule.
(2) background technology
Capsule typically refers to the internal semipermeable globular solids for hollow.It is generally used for encapsulation,
Catalysis, microreactor, detector, the aspect such as medicament slow release.Simultaneously can be by changing capsule wall
The semi-transparent performance of capsule is adjusted by feature.But the synthetic method of traditional capsule would ordinarily be encountered
Inefficient, it is difficult to amplify, the problem of the aspects such as controllability is poor.These problems upper limit to a great extent
Make the research and development of capsule.The material simultaneously preparing capsule is also various.Such as polymer,
Molecular sieve, metallo-organic compound etc. may be used to the preparation of capsule.Metal-organic framework materials is made
For a kind of coordination compound, metal node and organic ligand being combined into by coordinate bond, it has
Well chemical stability and heat stability, the most also have the following characteristics that huge specific surface area,
Micropore or the pore passage structure of mesoporous rank, the multiformity of chemical modification, gas Selective adsorption etc..
Therefore its by substantial amounts of for adsorbing/separating, catalysis, detector, medicament slow release, fuel cell from
The aspects such as sub-barrier film.
Metallic organic framework is also used for the preparation of capsule in recent years.De Vos et al. is closed by interface
One-tenth method has obtained Cu-BTC (one of metallic organic framework) capsule, and demonstrates this capsule and have
Selective penetrated property.Maspoch et al. has synthesized a series of metallic organic framework by spray drying method
Capsule, and it is applied to encapsulation, the aspect such as catalysis.Wang et al. is by adding in synthesis liquid
Polyvidone has synthesized the metallic organic framework capsule of Nano grade.But these capsules are unsupported.
Owing to the pliability of metallic organic framework is poor, and mechanical performance is not the most stable, the most unsupported
Metallic organic framework capsule may existing defects in lasting use.
Major part metal organic framework film is to be obtained above by metallic organic framework is grown on basement membrane
's.If therefore metallic organic framework can be grown in the substrate of hollow ball-shape, then can obtain
The metallic organic framework capsule supported, improves the stability of capsule.Simultaneously according to metal organic framework film
The condition of preparation understands, and the substrate of hollow ball-shape should have the following characteristics that 1) substrate should have
Well mechanical stability.2) substrate should be permeable.3) substrate should have in a large number
Heterogeneous nucleation site.Yeast cell wall can perfectly meet as a kind of natural hollow material
Above feature.Its as cell outermost layer protect structure have excellence mechanical stability and chemistry steady
Qualitative.Cell wall is close to and has whole-permeable simultaneously.Furthermore as the structure of organic-biological macromole composition,
It has substantial amounts of polar group, and therefore synthesis of organometallic frame capsule when, it can adsorbing metal
The part of organic bone precursor or metal ion form out-phase nucleus.If so cell wall being used for gold
The preparation belonging to organic backbone capsule can be greatly improved its range.
(3) summary of the invention
It is an object of the present invention to provide a kind of method preparing metallic organic framework capsule, utilize yeast thin
Cell wall is the synthetic method supporting substrate synthesis metallic organic framework-cell wall capsule.
The technical solution used in the present invention is:
The present invention provides a kind of method utilizing yeast synthesis metallic organic framework hollow structure capsule,
Described method is: (1) takes yeast cell wall and is suspended in solvent and makes cell wall suspension；Then will
Slaine or organic ligand make an addition in cell wall suspension, and 50-140 DEG C of stirring 6-24h is (preferably
50-100 DEG C of stirring 12h), centrifugal, take precipitation, it is thus achieved that cell wall containing metal ion or contain
The cell wall of machine part；Described solvent is water or organic solvent；(2) by the cell containing metal ion
Wall is scattered in organic ligand saline solution, or it is molten that the cell wall containing organic ligand is scattered in slaine
In liquid, 50-140 DEG C (preferably 50-100 DEG C) is slowly stirred crystallization, by the suspension after crystallization in room
The lower cooling of temperature, centrifugal (preferably centrifugal 5min under conditions of 5000 revs/min), remove supernatant,
Collect precipitate, i.e. obtain metallic organic framework-cell wall capsule；Different types of metal is had
The preparation of machine carcass capsule, the metal ion used is different with the solvent of organic ligand and employing；
When the cell wall containing metal ion is scattered in organic ligand saline solution, the organic bone of synthesized metal
Rack-layer is grown in the outer surface of cell wall；When the cell wall containing organic ligand is scattered in metal salt solution
Time middle, synthesized metallic organic framework layer growth is at the inner surface of cell wall.
Further, in step (1) yeast cell wall from beer yeast or bakery yeast.
Further, step (1) solvent is one of following: water, methanol, ethanol, ethylene glycol, third
Triol, ketopyrrolidine, N,N-Dimethylformamide, DMAC N,N' dimethyl acetamide, N, N-diethyl
Methanamide, pyridine, piperidines, furan, oxolane, dioxane or dimethyl sulfoxide.
Further, step (1) slaine is transition metal salt, preferably Zn (NO3)2·6H2O、
Cu(NO3)2·3H2O and FeCl3·3H2O, described organic ligand salt is Carboxylic acid ligand or imidazole ligands,
The final concentration of 20-400mmol/L of organic ligand salt, preferably 50-100 in described cell suspending liquid
Mmol/L, the final concentration of 20-400mmol/L of slaine, preferably 50-100mmol/L.
Further, step (2) organic ligand concentration of salt solution is 20-400mmol/L, preferably 50-100
Mmol/L, metal salt solution concentration is 20-400mmol/L, preferably 50-100mmol/L.
Yeast is utilized to synthesize metallic organic framework hollow structure capsule additionally, the present invention also provides for one
Method, described method is: yeast cell wall is scattered in slaine and organic ligand solvent is prepared
Mixed liquor in, 20-100 DEG C of stirring 6-24h (preferably 50-100 DEG C stirring 12h), crystallization, will knot
Suspension after crystalline substance at room temperature cools down, and under conditions of 5000 revs/min, centrifugal 5min, removes
Supernatant, collects precipitate, it is thus achieved that metallic organic framework-cell wall capsule；For different types of
The preparation of metallic organic framework capsule, the metal ion used and organic ligand and the solvent of employing
Different.Metallic organic framework layer growth prepared by the method is at the outer surface of cell wall.
Further, the final concentration of 20-400mmol/L of slaine, preferably 50-100 in mixed liquor
Mmol/L, most preferably 100mmol/L, the final concentration of 20-400mmol/L of described organic ligand,
Preferably 50-100mmol/L, most preferably 100mmol/L.
Further, described yeast cells is from beer yeast or bakery yeast.
Further, described solvent is one of following: water, methanol, ethanol, ethylene glycol, glycerol,
Ketopyrrolidine, DMF, N,N-dimethylacetamide, N, N-diethylformamide,
Pyridine, piperidines, furan, oxolane, dioxane or dimethyl sulfoxide.
Further, slaine is transition metal salt, preferably Zn (NO3)2·6H2O、FeCl3·6H2O or
Cu(NO3)2·6H2O, described organic ligand salt is Carboxylic acid ligand or imidazole ligands.
Metallic organic framework series of the present invention is: CuBTC (HKUST) series, ZIF series,
IRMOF series, MIL series, PCN series, FMOF series or BIO-MOF series.
The preparation method of yeast cell wall of the present invention is: take yeast powder (purchased from Angel Yeast share
Company limited) it is scattered in stirring and washing in deionized water, centrifugal, take bacterial sediment and be scattered in without water beetle
Alcohol, is uniformly mixed, centrifugal, is deposited in 50 DEG C and is dried, it is thus achieved that yeast cell wall.
Compared with prior art, advantages of the present invention:
1. yeast cell wall has natural hollow structure, and cell wall is permeable, has
Well for the potential quality of capsule synthesis.
2. the structure of the metallic organic framework synthesized by-cell wall capsule can according to synthesis condition and
Process is controlled.
3. the metallic organic framework synthesized by-cell wall capsule is ultra-thin, for tens nanometer to hundreds of
Nanometer, this feature can greatly be beneficial to the application of this capsule.
4. can be by controlling immersion part and the sequential control metallic organic framework layer of metal salt solution
It is to be grown in cell wall inner surface and outer surface.
5. metallic organic framework-cell wall the capsule of synthesis has good solvent resistance and very well
Mechanical strength.
(4) accompanying drawing explanation
Fig. 1 is the scanning electron microscope of the ZIF-8-yeast cell wall capsule of the embodiment of the present invention 1 synthesis
(A) with microscope figure (B).
Fig. 2 is the microscope of the MIL-53-yeast cell wall capsule of the 2-in-1 one-tenth of the embodiment of the present invention
Figure.
(5) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention
It is not limited to that:
Embodiment 1:
The synthesis of ZIF-8-yeast cell wall capsule
(1) take the yeast powder (purchased from Angel Yeast Co., Ltd) of 0.05g be scattered in from
Stirring and washing in sub-water, centrifugal rear standby.
(2) thalline that step (1) obtains is scattered in absolute methanol, is uniformly mixed, afterwards
Centrifugal, it is deposited in 50 DEG C and is dried, it is thus achieved that yeast cell wall.And this cell wall obtained is scattered in
In 10mL absolute methanol, it is thus achieved that yeast cell wall suspension.
(3) Zn (NO of 0.5mmol is taken3)2·6H2O is dissolved in the above-mentioned yeast cell wall of 10mL and suspends
Liquid, stirs 12h so that metal ion enters in the inner chamber of cell wall in the case of being placed in 50 DEG C,
Centrifugal, it is thus achieved that containing the cell wall of metal ion.
(4) the 2-methylimidazole methanol solution of 50mmol/L is configured, thin by containing metal ion
Cell wall is scattered in 50mmol/L2-Methylimidazole. methanol solution, stirs 12 in the case of 50 DEG C
Hour crystallization, allow crystallization after suspension cool down under room temperature (25 DEG C), afterwards 5000 turns/
Under conditions of minute, centrifugal 5min, removes supernatant, collects precipitate, it is thus achieved that and metallic organic framework-
Cell wall capsule, by 60 DEG C of dry for standby of capsule.
For the seriality of capsule and the mechanical performance of inspection institute's synthesis, in step (2)
Zn(NO3)2·6H22-methylimidazole methanol solution in O yeast cell wall suspension and step (3)
Adding rose dye, ultimate density is 0.1g/L, and so synthesized capsule can contain rose
Rare red molecule；Metallic organic framework containing rose-red molecule-cell wall capsule methanol is cleaned one
Time, it is placed in methanol stirring, simultaneously the rose-red content in detection methanol；Its content is almost nil；
When adding hydrochloric acid in methanol, solution reddens at once, and this shows that the capsule wall synthesized is continuous print.
Metallic organic framework containing rose-red molecule-cell wall capsule methanol is cleaned and is placed in methanol
Stirring ultrasonic, only have the rose-red of 20% to be released through ultraviolet-visual spectrometer detection, this shows this
Capsule has good mechanical strength, is anti-ultrasonic decomposition.Metallic organic framework-the cell wall obtained
Capsule is as shown in Figure 1.It can be seen that one layer of continuous print metallic organic framework is grown on yeast cell wall
Surface.The thickness of metallic framework is between 60-90nm.
Embodiment 2:
The synthesis of MIL-53-yeast cell wall capsule
(1) yeast powder taking 0.05g is scattered in deionized water, stirring and washing, centrifugal rear standby.
(2) thalline of acquisition is scattered in absolute methanol stirs and be centrifuged, precipitation N, N-diformazan
Base Methanamide cleans three times, and 60 DEG C are dried, it is thus achieved that yeast cell wall.The yeast cell wall of acquisition is divided
Dissipate in 10mL DMF, it is thus achieved that cell wall suspension.
(3) FeCl of 0.5mmol is taken3·6H2O is dissolved in 10mL above-mentioned cell wall suspension, is placed in
Stir 12h in the case of 100 DEG C so that metal ion enters in the inner chamber of cell wall, be centrifuged and obtain
Must be containing the cell wall of metal ion.
(4) configure the p-phthalic acid DMF solution of 50mmol/L, will contain
The cell wall of metal ion is scattered in this solution, stirred crystallization in the case of 100 DEG C, allows crystallization
After suspension at room temperature cool down, centrifugal 5min under conditions of 5000 revs/min, goes afterwards
Except supernatant, collect precipitate, it is thus achieved that metallic organic framework-cell wall capsule, by capsule 100 DEG C
Dry for standby.
The metallic organic framework obtained-cell wall capsule is as shown in Figure 2.It can clearly be seen that in film
Hollow structure.Detecting through method described in embodiment 1, in the case of stirring, rose-red discharges hardly,
Show that the capsule wall synthesized is continuous print；In the case of ultrasonic, the rose-red of only 10% is released
Putting, this shows that the capsule of synthesis has good mechanical strength, is anti-ultrasonic decomposition.The capsule of synthesis
The thickness of metallic organic framework layer is 40-60nm.
Embodiment 3:
The synthesis of CuBTC-yeast cell wall capsule
(1) yeast powder taking 0.05g is scattered in deionized water, stirring and washing, centrifugal rear standby.
(2) thalline of acquisition is scattered in absolute methanol, stirs and be centrifuged, precipitation deionization
Water cleans three times, it is thus achieved that yeast cell wall, 50 DEG C of drying for standby.And this cell wall obtained is divided
Dissipate in deionized water, it is thus achieved that cell wall suspension.
(3) Cu (NO of 0.5mmol is taken3)2·6H2O is dissolved in 10mL above-mentioned cell wall suspension,
12h is stirred so that metal ion enters in the inner chamber of cell wall in the case of being placed in 50 DEG C, from
The heart, it is thus achieved that containing the cell wall of metal ion.
(4) the trimesic acid ethanol solution of 50mmol/L is configured, thin by containing metal ion
Cell wall is scattered in this solution, in the case of 50 DEG C stir, crystallization, allow crystallization after suspension
At room temperature cooling down, centrifugal 5min under conditions of 5000 revs/min, removes supernatant afterwards,
Collect precipitate, it is thus achieved that metallic organic framework-cell wall capsule, by 60 DEG C of dry for standby of capsule.Warp
Method detection described in embodiment 1, in the case of stirring, rose-red discharges hardly；Ultrasonic
In the case of, the rose-red of only 15% is released；This shows that the capsule wall synthesized is continuous print, and
There is good mechanical strength, be anti-ultrasonic decomposition.The thickness of the capsule metallic organic framework layer of synthesis
For 70-100nm.
Embodiment 4:
The synthesis of ZIF-8-yeast cell wall capsule
(1) yeast powder taking 0.05g is scattered in deionized water, stirring and washing, centrifugal rear standby.
(2) thalline of acquisition is scattered in absolute methanol, stirs and be centrifuged, it is thus achieved that yeast cell wall,
By its 50 DEG C of drying for standby.And this cell wall obtained is scattered in 10mL methanol acquisition yeast
Cell wall suspension.
(3) 2-methylimidazole taking 1mmol is dissolved in 10mL above-mentioned cell wall suspension, is placed in
12h is stirred so that 2-methylimidazole enters in the inner chamber of cell wall in the case of 50 DEG C, centrifugal
Obtain the cell wall containing 2-methylimidazole.
(4) Zn (NO of 100mmol/L is configured3)2·6H2O methanol solution, will be containing 2-methyl
The cell wall of imidazoles is scattered in Zn (NO3)2·6H2In O methanol solution, stir in the case of 50 DEG C
Crystallization in 12 hours, allows the suspension after crystallizing at room temperature cool down, afterwards at 5000 revs/min
Under the conditions of centrifugal 5min, remove supernatant, collect precipitate, it is thus achieved that metallic organic framework-cell wall
Capsule, by 60 DEG C of dry for standby of capsule.Detect through method described in embodiment 1, in the situation of stirring
Under, rose-red discharges hardly；In the case of ultrasonic, the rose-red of only 12% is released；
This shows that the capsule wall synthesized is continuous print, and has good mechanical strength, is anti-ultrasonic decomposition.
The thickness of the capsule metallic organic framework layer of synthesis is 100-130nm.
Embodiment 5:
The synthesis of ZIF-8-yeast cell wall capsule
(1) yeast powder taking 0.05g is scattered in deionized water, stirring and washing, centrifugal rear standby.
(2) thalline of acquisition is scattered in absolute methanol, stirs and be centrifuged, it is thus achieved that yeast cell wall,
50 DEG C of drying for standby.
(3) 2-methylimidazole and the 1mmol Zn (NO of 1mmol are taken3)2·6H2O is dissolved in 10ml first
In alcohol, the cell wall of preparation is scattered in above-mentioned methanol solution, stirring knot in the case of 50 DEG C
Crystalline substance, allows the suspension after crystallizing at room temperature cool down, centrifugal under conditions of 5000 revs/min afterwards
5min, removes supernatant, collects precipitate, it is thus achieved that metallic organic framework-cell wall capsule, by glue
60 DEG C of dry for standby of capsule.
The seriality of capsule and mechanical performance, the methanol solution in step (3) for inspection institute's synthesis
Adding rose dye, ultimate density is 0.1g/L, and so synthesized capsule can contain Flos Rosae Rugosae
Red molecule；Metallic organic framework containing rose-red molecule-cell wall capsule methanol is cleaned one time,
It is placed in methanol solvate stirring, simultaneously the rose-red content in detection methanol solvate；Its content is almost
It is zero；When adding hydrochloric acid in methanol solvate, solution reddens at once, and this shows the capsule wall of synthesis
It it is continuous print.After metallic organic framework containing rose-red molecule-cell wall capsule is cleaned with methanol
It is placed in methanol solvate and stirs ultrasonic, released through the rose-red of ultraviolet-visual spectrometer detection only 6%
Putting, this shows that this capsule has good mechanical strength, is anti-ultrasonic decomposition.The thickness of metallic framework
Between 300-500nm.
Claims (10)
1. the method utilizing yeast synthesis metallic organic framework hollow structure capsule, it is characterised in that
Described method is: (1) takes yeast cell wall and is suspended in solvent and makes cell wall suspension；Then by gold
Belong to salt or organic ligand adds in cell wall suspension, 50-140 DEG C of stirring 6-24h, centrifugal, take precipitation,
Obtain the cell wall containing metal ion or the cell wall containing organic ligand；Described solvent is water or organic molten
Agent；(2) cell wall containing metal ion is scattered in organic ligand solution, or organic joining will be contained
The cell wall of body is scattered in metal salt solution, 50-140 DEG C of stirred crystallization, is existed by the suspension after crystallization
Cool down under room temperature, centrifugal, remove supernatant, collect precipitate, i.e. obtain metallic organic framework-cell wall
Capsule.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 1
Method, it is characterised in that in step (1), yeast cell wall is from beer yeast or bakery yeast.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 1
Method, it is characterised in that step (1) solvent is one of following: water, methanol, ethanol, ethylene glycol, the third three
Alcohol, ketopyrrolidine, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N-diethylformamide,
Pyridine, piperidines, furan, oxolane, dioxane or dimethyl sulfoxide.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 1
Method, it is characterised in that step (1) slaine is transition metal salt, described organic ligand be Carboxylic acid ligand or
Imidazole ligands, the final concentration of 20-400mmol/L of organic ligand in described cell suspending liquid, slaine is the denseest
Degree is 20-400mmol/L.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 1
Method, it is characterised in that step (2) organic ligand solution concentration is 20-400mmol/L, metal salt solution
Concentration is 20-400mmol/L.
6. the method utilizing yeast synthesis metallic organic framework hollow structure capsule, it is characterised in that
Described method is: take yeast cell wall be scattered in slaine and organic ligand mixture solvent preparation
In mixed liquor, 20-100 DEG C of stirred crystallization, the suspension after crystallization is at room temperature cooled down, centrifugal,
Remove supernatant, collect precipitate, i.e. obtain metallic organic framework-cell wall capsule.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 6
Method, it is characterised in that the final concentration of 20-400mmol/L of slaine in mixed liquor, organic ligand is final concentration of
20-400mmol/L。
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 6
Method, it is characterised in that described yeast cell wall is from beer yeast or bakery yeast.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 6
Method, it is characterised in that described solvent is one of following: water, methanol, ethanol, ethylene glycol, glycerol,
Ketopyrrolidine, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N-diethylformamide, pyrrole
Pyridine, piperidines, furan, oxolane, dioxane or dimethyl sulfoxide.
Utilize the side of yeast synthesis metallic organic framework hollow structure capsule the most as claimed in claim 6
Method, it is characterised in that slaine is transition metal salt, organic ligand is Carboxylic acid ligand or imidazole ligands.
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| EP0460945B1 (en) * | 1990-06-05 | 1995-10-11 | Mitsubishi Paper Mills, Ltd. | Process for producing microcapsules |
| GB9509937D0 (en) * | 1995-05-17 | 1995-07-12 | Cpc International Inc | Encapsulated product |
| JP2777981B2 (en) * | 1995-09-12 | 1998-07-23 | 工業技術院長 | Hollow spherical material composed of chitosan-containing fiber and method for producing the same |
| GB2424408A (en) * | 2005-03-24 | 2006-09-27 | Micap Plc | Encapsulation using microbial cells |
| CN100389754C (en) * | 2005-10-25 | 2008-05-28 | 天津大学 | Microcapsule preparing process utilizing waste beer yeast cell as wall material |
| CN100544815C (en) * | 2007-07-01 | 2009-09-30 | 石国荣 | A kind of method of utilizing the microcapsule wall material of yeast cell to prepare safety non-toxic good property |
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