CN107640783B - Porous regular dodecahedral ZnO and application thereof as lecithin adsorption material - Google Patents

Porous regular dodecahedral ZnO and application thereof as lecithin adsorption material Download PDF

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CN107640783B
CN107640783B CN201710962138.3A CN201710962138A CN107640783B CN 107640783 B CN107640783 B CN 107640783B CN 201710962138 A CN201710962138 A CN 201710962138A CN 107640783 B CN107640783 B CN 107640783B
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lecithin
zno
regular dodecahedron
porous regular
adsorbent material
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CN107640783A (en
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冼燕萍
梁明
王斌
吴玉銮
王莉
赵晓娟
侯向昶
吴益阳
陈嘉慧
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GUANGZHOU QUALITY SUPERVISION AND TESTING INSTITUTE
Zhongkai University of Agriculture and Engineering
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GUANGZHOU QUALITY SUPERVISION AND TESTING INSTITUTE
Zhongkai University of Agriculture and Engineering
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Abstract

The invention relates to porous regular dodecahedral ZnO and application thereof as a lecithin adsorption material. The porous regular dodecahedral ZnO can be used as a lecithin adsorption material, and selective adsorption and enrichment can be performed on lecithin through characteristic Lewis acid-base reaction and by combining the advantages of a nano material and a metal organic framework material, so that the adsorption efficiency can reach 80%.

Description

Porous regular dodecahedron ZnO and its application as lecithin adsorbent material
Technical field
The present invention relates to food and Material Field, more particularly to a kind of porous regular dodecahedron ZnO and its as lecithin The application of rouge adsorbent material.
Background technique
Phosphatidyl choline (PC) is the most abundant phosphatide for forming cell membrane, because content is very high in yolk, Gu also known as It is lecithin.Lecithin has very high nutritive value.But because containing many unsaturated fatty acids in structure, show as pole It is oxidizable, easy to moisture absorption.Due to the limitation of technology, it is more difficult to separate and extract from yolk and other biological sample.
It is separated from yolk since lecithin is more difficult, it is less to the development and utilization of egg yolk lecithin currently on the market;By It is removed from other biological sample in lecithin is more difficult, when UPLC is tested and analyzed in the biological sample containing lecithin, lecithin The presence of rouge influences whether the response of other substances.
For these reasons, it is necessary to selective absorption be carried out to lecithin, and then realize above-mentioned application.However, at present The research of selective absorption lecithin just starts, also and few for adsorbing the material of lecithin.In currently existing scheme, make With micron order TiO2With ZrO2Material, selective absorption and enrichment phosphatide, lecithin and cephalin.But by its granular size Limitation, adsorption efficiency is high.
So studying a kind of new material, selective absorption and enrichment lecithin are of great significance.
Summary of the invention
Based on this, it is necessary in view of the above-mentioned problems, providing a kind of porous regular dodecahedron ZnO and its being adsorbed as lecithin The application of material, to realize simple, the efficient absorption and enrichment to lecithin.
The present invention provides a kind of porous regular dodecahedron ZnO.
The porous regular dodecahedron ZnO skeleton is having a size of 400-900nm in one of the embodiments, by size of microcrystal It is formed for the ZnO particle of 20-80nm.
It is a further object to provide the preparation method of above-mentioned porous regular dodecahedron ZnO a kind of, including it is following Step:
Under air atmosphere, metal organic framework ZIF-8 is risen to 450-500 DEG C with the rate of 2-3 DEG C/min, keeps the temperature 2- 3h obtains above-mentioned porous regular dodecahedron ZnO.
Metal organic framework ZIF-8, i.e. zeolite imidazole class framework material -8, are porous crystalline materials.
It is a further object to provide above-mentioned porous regular dodecahedron ZnO answering as lecithin adsorbent material With.
It is a further object to provide a kind of lecithin adsorbent material, including it is described in claim 1 it is porous just Dodecahedron ZnO.
It is a further object to provide above-mentioned lecithin adsorbent materials to contain lecithin using UPLC detection Application in biological sample.
It is a further object to provide a kind of UPLC detection methods of sample containing lecithin, including following step Suddenly:
Sample pre-treatments:Sample containing lecithin is handled using lecithin adsorbent material as claimed in claim 4;
Conventional steps carry out UPLC detection.
It is a further object to provide above-mentioned lecithin adsorbent materials to extract the application in egg yolk lecithin.
It is a further object to provide a kind of extracting methods of egg yolk lecithin, include the following steps:
Absorption:Lecithin in yolk is enriched with using lecithin adsorbent material as claimed in claim 4.
Parsing:Conventional resolution is carried out to the lecithin adsorbent material after enrichment lecithin.
Compared with existing scheme, the invention has the advantages that:
The ZnO of above-mentioned porous regular dodecahedron has bigger serface, and this material has metallo-organic framework, The disadvantage that common nano material can be overcome easy to reunite.Meanwhile ZnO is amphoteric metal oxide, the spy with Lewis Acids and Bases Point has higher affinity to phosphate, can be in conjunction with the phosphate group on lecithin.
The ZnO of above-mentioned porous regular dodecahedron can be reacted by the Lewis Acids and Bases of feature, in combination with nano material Selective absorption and enrichment are carried out to lecithin with the advantages of metal-organic framework materials.
The present invention verifies the performance of phosphatide in above-mentioned material selective absorption yolk, the results showed that, above-mentioned ovum The adsorption efficiency of phosphatide adsorbent material can reach 80%.
For above-mentioned adsorbent material using metal organic framework ZIF-8 as presoma, preparation method is simple, can be located in batches Reason provides important scientific basis for the utilization of lecithin.
It on the one hand, will before using sample of the UPLC analysis measurement containing lecithin using adsorbent material of the present invention Lecithin is removed from sample, and testing efficiency theoretically can be improved.
On the other hand, above-mentioned lecithin adsorbent material is applied to extract in egg yolk lecithin by the present invention, can be further Above-mentioned adsorbent material after the completion of enrichment is parsed, the higher egg yolk lecithin of purity is obtained, is mentioned for the extraction of lecithin For a kind of new approaches.
Detailed description of the invention
Fig. 1 is the XRD spectrum of ZIF-8 presoma;
Fig. 2 is the SEM spectrum of ZIF-8 presoma;
Fig. 3 is the XRD spectrum of porous regular dodecahedron ZnO;
Fig. 4 is the SEM spectrum of porous regular dodecahedron ZnO;
Fig. 5 is the UPLC map of 1 mesolecithal lecithin standard product of embodiment;
Fig. 6 is the UPLC map of 1 mesolecithal lecithin extract liquor of embodiment;
Fig. 7 is the UPLC map that the supernatant after 12h is handled in embodiment 1;
Fig. 8 is the UPLC map of the supernatant after handling for 24 hours in embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment to the material and the preparation method and application thereof of selective absorption lecithin of the invention It is described in further detail.
Embodiment 1
A kind of porous regular dodecahedron ZnO, preparation method include the following steps:
(1) methylimidazole of 6.6g, the Zn (NO of 3g are weighed3)2·6H2O is added separately in 140mL methanol solution, Stirring sufficiently, obtains methylimidazole solution and zinc nitrate solution, methylimidazole solution is poured into the solution of zinc nitrate, in room The lower stirring of temperature for 24 hours, is centrifugally separating to obtain solid, again with methanol solution is cleaned three times, is put into thermostatic drying chamber, at 80 DEG C overnight Resulting product, that is, presoma after drying.
Presoma is characterized, is as shown in Figure 1, 2 the XRD spectrum and SEM spectrum of presoma.In Fig. 1, abscissa is Twice of the incident angle of X-ray, ordinate are the intensity after diffraction.Fig. 1 confirms the presence of ZIF-8 presoma;In Fig. 2, ZIF-8 presoma is in Polyhedral Particles shape structure, and particle surface is smooth, and partial size is about 1 μm or so.
(2) above-mentioned ZIF-8 presoma is put in crucible and is placed in tube furnace, under air atmosphere, with 2 DEG C/min's Rate rises to 450 DEG C, and keeps the temperature 2h, obtains white powder.
White powder is characterized, is as shown in Figure 3,4 the XRD spectrum and SEM spectrum of white powder.In Fig. 3, ZIF- The characteristic absorption peak of 8 presomas disappears, and new absorption peak is consistent with ZnO standard feature absorption peak, and peak type is sharp, illustrates through excessively high After temperature calcining, ZIF-8 presoma is changed into ZnO, and the ingredient of white powder is ZnO;In Fig. 4, size of microcrystal is received for 20-80nm The ZnO particle of rice forms porous regular dodecahedron structure, and skeleton is having a size of 400-900nm.Illustrate white powder be it is porous just The ZnO of dodecahedron.
The above-mentioned porous regular dodecahedron ZnO being prepared is applied as lecithin adsorbent material.Method is as follows:
(1) extraction of egg yolk lecithin
2.0g yolk is weighed in 10mL colorimetric cylinder, sequentially adds 5mL sample extracting solution (volume ratio 9:1 ethyl alcohol and Aqueous solution), 5mL n-hexane is vortexed and mixes.1200r/min is centrifuged 2min, removes n-hexane layer.Ethyl alcohol is added into colorimetric cylinder, 1200r/min is centrifuged 2min, and 10mL is settled to after taking supernatant liquor to filter, and is vortexed and mixes, obtains egg yolk lecithin extract liquor.
(2) absorption of lecithin
Egg yolk lecithin extract liquor 5mL is taken, the porous regular dodecahedron ZnO of 0.1g is added, is stirred at room temperature, reacts respectively 12,24h.1200r/min is centrifuged 2min, collects supernatant, repeated centrifugation 3 times, obtains supernatant A, B.
UPLC characterization is carried out respectively to above-mentioned egg yolk lecithin extract liquor and supernatant A, B
(1) high-efficient liquid phase chromatogram determining condition is as follows:
Chromatographic column:BEH HILIC 50mm × 2.1mm, 1.7 μm of columns;
Column temperature:30℃;
Mobile phase:Volume ratio is 60:40 methanol and aqueous isopropanol, and pH=8 is adjusted with ammonium hydroxide;
Flow velocity:0.2mL/min, isocratic elution;
Sampling volume:2μL;
Detector:PDA detector, scanning wavelength 190-250nm, quantitative wavelength 205nm.
(2) configuration of egg yolk lecithin standard items
0.2g egg yolk lecithin standard items are weighed in 10mL colorimetric cylinder, sequentially add 5mL sample extraction solvent (volume ratio It is 9:1 ethyl alcohol and aqueous solution), 5mL n-hexane is vortexed and mixes.1200r/min is centrifuged 2min, removes n-hexane layer.To colorimetric Ethyl alcohol is added in pipe and is settled to 10mL, obtains the egg yolk lecithin standard solution that concentration is 0.02g/mL, is vortexed and mixes, obtain yolk Lecithin standard product solution.
(3) accurate respectively to draw 2 μ L egg yolk lecithin standard items, 2 μ L egg yolk lecithin extract liquors, the supernatant A of 2 μ L, 2 μ L supernatant B injects liquid chromatograph according to high effective liquid chromatography for measuring and respectively obtains high-efficient liquid phase chromatogram 5- Fig. 8, The size of comparison chromatographic peak area calculates adsorption efficiency.
(4) adsorption effect is analyzed:It is calculated by figure 5-8, the lecithin concentration C of egg yolk lecithin extract liquor= 0.019g/ml;After handling 12h, concentration C=0.013g/ml of lecithin, adsorption efficiency η=31.6% in supernatant A;Processing After for 24 hours, concentration C=0.0038g/ml of lecithin, adsorption efficiency η=80.0% in supernatant B.
By in above-mentioned test analysis, it is known that, above-mentioned lecithin adsorbent material can effectively adsorb lecithin.
In biological sample containing lecithin, the presence of lecithin will affect the efficient liquid phase of other substances in biological sample Chromatography detection, and be difficult to remove lecithin from biological sample.Therefore, above-mentioned lecithin adsorbent material is applied to containing ovum In the biological sample UPLC detection of phosphatide.
Embodiment 2
It in the sample containing lecithin, is removed from sample since lecithin is more difficult, detects it when sample carries out UPLC When his ingredient, the presence of lecithin can influence the accuracy of test result to a certain extent.The present embodiment provides one kind to contain The UPLC detection method of lecithin blood serum sample, includes the following steps:
Pre-treatment is carried out to the blood serum sample containing lecithin:Above-mentioned lecithin adsorbent material is put into containing lecithin In blood serum sample, stirring is for 24 hours.
Routine UPLC detection is carried out to the blood serum sample after the completion of absorption.
The present embodiment is before using blood serum sample of the UPLC analysis measurement containing lecithin, by above-mentioned lecithin adsorbent material It is placed in the blood serum sample containing lecithin and stirs for 24 hours, lecithin can be removed from sample, improve the effect of test other compositions Rate.
Embodiment 3
Above-mentioned lecithin adsorbent material is applied to the method in the extraction of egg yolk lecithin the present embodiment provides a kind of, is walked It is rapid as follows:
Absorption:Egg yolk lecithin is enriched with using above-mentioned adsorbent material.Above-mentioned lecithin adsorbent material is placed in egg In yellow lecithin extract liquor, after adjusting pH≤7, stirring is for 24 hours.
Parsing:Conventional resolution is carried out to the lecithin adsorbent material after enrichment lecithin, obtains the higher egg of purity Yellow lecithin.
This method first adsorbs egg yolk lecithin, then parses to solid precipitating, obtains the higher egg of purity Yellow lecithin provides a kind of new approaches for the extraction of lecithin.
Principle is as follows:Under different pH value, ZnO can show as lewis acid or lewis base.In acid condition, Zinc atom is positively charged to show as lewis acid, can be with anion binding, and the lecithin with phosphate group is in the item of pH≤7 Under part, phosphate group is all negatively charged, so ZnO can achieve the purpose that selective absorption in conjunction with lecithin;And in alkalinity Under the conditions of, Zn atom is then negatively charged to show as lewis base, and the phosphate group of lecithin be also it is negatively charged, ZnO will at this time It is separated with electronegative phosphate group, detaches lecithin from porous ZnO, achieve the purpose that parsing.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (11)

1. application of the porous regular dodecahedron ZnO as lecithin adsorbent material.
2. application according to claim 1, which is characterized in that the porous regular dodecahedron ZnO skeleton is having a size of 400- 900nm is made of the ZnO particle that size of microcrystal is 20-80nm.
3. application according to claim 1, which is characterized in that the preparation method of the porous regular dodecahedron ZnO includes Following steps:
Under air atmosphere, organometallic skeletal ZIF-8 is risen to 450-500 DEG C with the rate of 2-3 DEG C/min, keeps the temperature 2-3h, Obtain the porous regular dodecahedron ZnO.
4. lecithin adsorbent material is using the application in sample of UPLC (ultra performance liquid chromatography) detection containing lecithin;
The lecithin adsorbent material includes porous regular dodecahedron ZnO.
5. application according to claim 4, which is characterized in that the porous regular dodecahedron ZnO skeleton is having a size of 400- 900nm is made of the ZnO particle that size of microcrystal is 20-80nm.
6. application according to claim 4, which is characterized in that the preparation method of the porous regular dodecahedron ZnO includes Following steps:
Under air atmosphere, organometallic skeletal ZIF-8 is risen to 450-500 DEG C with the rate of 2-3 DEG C/min, keeps the temperature 2-3h, Obtain the porous regular dodecahedron ZnO.
7. a kind of UPLC detection method of the sample containing lecithin, which is characterized in that include the following steps:
Sample pre-treatments:Sample containing lecithin is handled using lecithin adsorbent material as claimed in claim 4;
UPLC detection is carried out according to a conventional method.
8. lecithin adsorbent material is extracting the application in egg yolk lecithin;
The lecithin adsorbent material includes porous regular dodecahedron ZnO.
9. application according to claim 8, which is characterized in that the porous regular dodecahedron ZnO skeleton is having a size of 400- 900nm is made of the ZnO particle that size of microcrystal is 20-80nm.
10. application according to claim 8, which is characterized in that the preparation method of the porous regular dodecahedron ZnO includes Following steps:
Under air atmosphere, organometallic skeletal ZIF-8 is risen to 450-500 DEG C with the rate of 2-3 DEG C/min, keeps the temperature 2-3h, Obtain the porous regular dodecahedron ZnO.
11. a kind of extracting method of egg yolk lecithin, which is characterized in that include the following steps:
Absorption:Lecithin in yolk is enriched with using lecithin adsorbent material according to any one of claims 8;
Parsing:Conventional resolution is carried out to the lecithin adsorbent material after enrichment lecithin.
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