CN107126925B - Magnetic nano material and application thereof in anegliptin drug detection - Google Patents
Magnetic nano material and application thereof in anegliptin drug detection Download PDFInfo
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- CN107126925B CN107126925B CN201710440501.5A CN201710440501A CN107126925B CN 107126925 B CN107126925 B CN 107126925B CN 201710440501 A CN201710440501 A CN 201710440501A CN 107126925 B CN107126925 B CN 107126925B
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 29
- 239000003814 drug Substances 0.000 title claims abstract description 27
- 238000001514 detection method Methods 0.000 title claims abstract description 26
- 229940079593 drug Drugs 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012153 distilled water Substances 0.000 claims abstract description 55
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 24
- 238000010992 reflux Methods 0.000 claims abstract description 20
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 16
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003463 adsorbent Substances 0.000 claims description 24
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 24
- 239000006228 supernatant Substances 0.000 claims description 21
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000012488 sample solution Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 4
- 239000007974 sodium acetate buffer Substances 0.000 claims 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
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- 230000000694 effects Effects 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 238000001334 liquid-phase micro-extraction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- 238000002470 solid-phase micro-extraction Methods 0.000 description 2
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- 101710137760 Malonyl-CoA-acyl carrier protein transacylase, mitochondrial Proteins 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000001172 liquid--solid extraction Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005220 pharmaceutical analysis Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a novel magnetic nano material and application thereof in anegliptin drug detection. The preparation method of the novel magnetic nano material comprises the following steps: (1) taking a proper amount of distilled water, adding C70Introducing nitrogen or argon into fullerene, ferrous sulfate heptahydrate and anhydrous ferric chloride, stirring for 15-20 minutes, heating to a reflux temperature, keeping refluxing for 20-30 minutes, cooling to 85-90 ℃, maintaining the temperature (85-90 ℃) and dropwise adding ammonia water, continuously stirring for reacting for 1-1.5 hours, wherein the reaction liquid is in a black turbid state, naturally cooling to room temperature, standing for 0.5 hour, and then adsorbing and separating by using a magnet to obtain a black solid; (2) washing the black solid obtained in the step (1) with distilled water for 3-5 times, and vacuum drying at 60 ℃ for 12-24h to obtain black solid powder, namely magnetic C70A fullerene nanomaterial.
Description
Technical Field
The invention belongs to the field of material and drug analysis, and particularly relates to a novel magnetic nano material and application thereof in aneogliptin drug detection.
Background
Since the concentration of a drug in the living body, particularly in the serum, is directly related to the drug effect. Therefore, from the aspects of clinical application and drug safety evaluation, a simple, sensitive and accurate analysis method for detecting the content of the anegliptin in the biological body fluid and the drug is needed to be established. Currently, widely applied drug analysis methods include high performance liquid chromatography, thin layer chromatography, ion exchange chromatography and the like. At present, few documents are reported about the method for measuring the content of the anergol, and the method for measuring the content of the anergol by using an ultraviolet-visible spectrophotometry is not reported.
In the pharmaceutical analysis, the separation and enrichment of the sample, namely the pretreatment of the sample, play a key role. The separation and enrichment are used for separating and extracting the analyte from the matrix, and simultaneously, the purpose of concentrating the medicine is achieved, so that the effects of improving the accuracy and the sensitivity can be realized. With the development and progress of the times, the separation and enrichment technology is greatly developed at present. Common separation and enrichment methods include extraction, including liquid-liquid extraction (LLE), solid-phase extraction (SPE), solid-phase microextraction (SPME), liquid-phase microextraction (LPME), and dispersion liquid-liquid microextraction (DLLME). When the biological fluid is measured, because the components in the body fluid are complex, the components are not easy to separate to form interference, and the content of the medicine to be measured is generally low, the separation and enrichment of the sample are particularly important. The reasonable and efficient separation and enrichment technology is adopted to separate and extract the low-content drug to be detected from the complex biological matrix, so that the method is used for quickly and accurately carrying out quantitative analysis and is an important content of in-vivo drug analysis. In view of the advantages and disadvantages of various separation techniques, there are currently significant improvements to solid phase extraction techniques, such as magnetic solid phase extraction techniques. The Solid Phase Extraction (SPE) developed at the earliest is also called liquid-solid extraction, and is a sample separation and enrichment technology developed from the early 70 s in the 20 th century. The magnetic solid phase extraction is a novel and environment-friendly sample pretreatment analysis technology developed on the basis of SPE, and the analytes are extracted more efficiently by utilizing the adsorption effect of the magnetic nano material. The magnetic nano material can be used as an adsorbent for magnetic solid phase extraction due to the combination of the magnetic responsiveness and the characteristics of the nano particles. Compared with the traditional sample pretreatment technologies such as solid phase extraction, solvent extraction, ultrasonic extraction and the like, the application of the magnetic solid phase extraction greatly simplifies the sample pretreatment process and is easy to realize phase separation.
Magnetic Carrier Technology (MCT) was first reported by Robinson et al. In 1973, the synthesis of micro (or nano) magnetic carriers has attracted a wide range of interest. A unique and attractive property of MCTs is that magnetic nanoparticles can be easily separated from a sample solution by applying an external magnetic field. These particles are superparamagnetic, which means that they can be easily attracted by magnets, but do not retain magnetism after the field is removed. This property makes them particularly suitable for sample preparation, since centrifugation or filtration of the sample after extraction is not required, as compared to non-magnetic adsorbents.
Disclosure of Invention
The invention provides a magnetic C70Fullerene nano material (abbreviated as C)70-Fe3O4) The preparation method is characterized by comprising the following steps:
(1) taking a proper amount of distilled water, adding C70Introducing nitrogen or argon into fullerene, ferrous sulfate heptahydrate and anhydrous ferric chloride, stirring for 15-20 minutes, heating to a reflux temperature, keeping refluxing for 20-30 minutes, cooling to 85-90 ℃, maintaining the temperature (85-90 ℃) and dropwise adding ammonia water, continuously stirring for reacting for 1-1.5 hours, wherein the reaction liquid is in a black turbid state, naturally cooling to room temperature, standing for 0.5 hour, and then adsorbing and separating by using a magnet to obtain a black solid;
(2) washing the black solid obtained in the step (1) with distilled water for 3-5 times, and vacuum drying at 60 ℃ for 12-24h to obtain black solid powder, namely magnetic C70Fullerene nano material (abbreviated as C)70-Fe3O4)。
Distilled water and C in step (1)70The dosage of fullerene, ferrous sulfate heptahydrate, anhydrous ferric chloride and ammonia water is 0.1mmol C per 100mL distilled water70Fullerene, 0.2mmol ferrous sulfate heptahydrate, 0.4mmol anhydrous ferric chloride and 3-5mL ammonia water; the distilled water is preferably distilled water after ultrasonic treatment.
The present invention provides the above magnetic C70Fullerene nano material (abbreviated as C)70-Fe3O4) Is characterized by the preparation methodThe method comprises the following steps:
(1) taking a proper amount of distilled water, adding C70Introducing nitrogen or argon into fullerene, ferrous sulfate heptahydrate and anhydrous ferric chloride, stirring for 15-20 minutes, heating to a reflux temperature, keeping refluxing for 20-30 minutes, cooling to 85-90 ℃, maintaining the temperature (85-90 ℃) and dropwise adding ammonia water, continuously stirring for reacting for 1-1.5 hours, wherein the reaction liquid is in a black turbid state, naturally cooling to room temperature, standing for 0.5 hour, and then adsorbing and separating by using a magnet to obtain a black solid;
(2) washing the black solid obtained in the step (1) with distilled water for 3-5 times, and vacuum drying at 60 ℃ for 12-24h to obtain black solid powder, namely magnetic C70A fullerene nanomaterial.
Distilled water and C in step (1)70The dosage of fullerene, ferrous sulfate heptahydrate, anhydrous ferric chloride and ammonia water is 0.1mmol C per 100mL distilled water70Fullerene, 0.2mmol ferrous sulfate heptahydrate, 0.4mmol anhydrous ferric chloride and 3-5mL ammonia water; the distilled water is preferably distilled water after ultrasonic treatment.
In another embodiment of the present invention, the magnetic property C is70Fullerene nano material (abbreviated as C)70-Fe3O4) The application of the anegliptin in drug detection is disclosed. C70-Fe3O4And functions as a solid phase extraction adsorbent.
Magnetic C70Fullerene nano material C70-Fe3O4The application of the anergoid in detecting the concentration of the anergoid in a sample is characterized by comprising the following steps:
(1) and (3) extraction: 1.0mL of pH 3.0 acetic acid-sodium acetate (HAc-NaAc) buffer solution, a proper amount of sample solution to be detected and 10-20mg of C are respectively added into a 10.0mL centrifuge tube70-Fe3O4Diluting with distilled water to 10mL, shaking at room temperature for 10-15min, standing, and separating C by magnet adsorption70-Fe3O4After the supernatant solution is clear and transparent, taking the supernatant and detecting by using an ultraviolet-visible spectrophotometer;
(2) and (3) elution: adsorbing and separating C obtained in the step (1) by using a magnet70-Fe3O4Placing in a centrifuge tube, adding anhydrous ethanol, diluting to desired volume, shaking, oscillating at room temperature for 20-30min, standing, and separating with magnet to obtain C70-Fe3O4And (4) settling, and taking the supernatant to detect by using an ultraviolet-visible spectrophotometer after the supernatant is clear and transparent.
Another embodiment of the present invention provides the above magnetic C70Fullerene nano material C70-Fe3O4The application of the solid phase extraction adsorbent in preparation of the solid phase extraction adsorbent, in particular to the application in preparation of the solid phase extraction adsorbent for detecting the Annelliptin medicament.
The constant volume of the invention refers to adding a solvent (absolute ethyl alcohol) to a scale (a centrifugal tube).
The invention has the advantages that: firstly, preparing magnetic C70Fullerene nano material C70-Fe3O4Detection of Annelliptin drugs as solid phase extraction adsorbents, C70-Fe3O4Compared with the common magnetic solid phase extraction adsorbent, the magnetic solid phase extraction adsorbent has the characteristics of strong adsorbability on the anegliptin and easy elution; ② C prepared by the invention70-Fe3O4The particle diameter is 5-8nm, and C is used70The cage structure of the compound can be fully contacted with an anegliptin drug to form a pi-pi conjugated system, a hydrogen bond and the like.
Drawings
FIG. 1 magnetic C prepared in example 170Fullerene nano material (abbreviated as C)70-Fe3O4) TEM image of
FIG. 2 Standard working Curve of Annelliptin concentration and Absorbance
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
Adding 0.2m into 200mL of distilled watermol C70Fullerene, 0.4mmol of ferrous sulfate heptahydrate and 0.8mmol of anhydrous ferric chloride are introduced with nitrogen and stirred for 15 minutes, then heated to the reflux temperature, kept refluxing for 20-30 minutes, cooled to 85-90 ℃, kept at the temperature (85-90 ℃) and dropwise added with ammonia water (6mL), continuously stirred and reacted for 1-1.5 hours, the reaction solution is in a black turbid state, naturally cooled to the room temperature, kept standing for 0.5 hour, and then adsorbed and separated by a magnet to obtain a black solid; washing with distilled water for 3-5 times, vacuum drying at 60 deg.C for 12 hr to obtain black solid powder, i.e. magnetic C70Fullerene nano material (abbreviated as C)70-Fe3O4Fig. 1, hereinafter referred to as product a); the distilled water used in this example was distilled water after ultrasonic treatment.
Example 2
100mL of distilled water was added with 0.1mmol of C70Fullerene, 0.2mmol of ferrous sulfate heptahydrate and 0.4mmol of anhydrous ferric chloride are introduced with argon gas, stirred for 20 minutes, heated to the reflux temperature, kept refluxing for 20-30 minutes, cooled to 85-90 ℃, kept at the temperature (85-90 ℃) and dropwise added with ammonia water (5mL), continuously stirred for reaction for 1-1.5 hours, the reaction solution is in a black turbid state, naturally cooled to the room temperature, kept standing for 0.5 hour, and then adsorbed and separated by a magnet to obtain a black solid; washing with distilled water for 3-5 times, vacuum drying at 60 deg.C for 24 hr to obtain black solid powder, i.e. magnetic C70Fullerene nano material (abbreviated as C)70-Fe3O4SEM picture is consistent with that of figure 1, hereinafter referred to as product B); the distilled water used in this example was distilled water after ultrasonic treatment.
Example 3
Adding 0.2mmol of graphene, 0.4mmol of ferrous sulfate heptahydrate and 0.8mmol of anhydrous ferric chloride into 200mL of distilled water, introducing nitrogen, stirring for 15 minutes, heating to reflux temperature, keeping refluxing for 20-30 minutes, cooling to 85-90 ℃, maintaining the temperature (85-90 ℃) and dropwise adding ammonia water (6mL), continuously stirring for reacting for 1-1.5 hours until the reaction solution is in a black turbid state, naturally cooling to room temperature, standing for 0.5 hour, and then adsorbing and separating by using a magnet to obtain a black solid; washing with distilled water for 3-5 times, and vacuum drying at 60 deg.C for 12h to obtain black solid powder, i.e. magnetic graphene material (hereinafter referred to as product C); the distilled water used in this example was distilled water after ultrasonic treatment.
Example 4
Adding 0.4mmol of ferrous sulfate heptahydrate and 0.8mmol of anhydrous ferric chloride into 200mL of distilled water, introducing nitrogen, stirring for 15 minutes, heating to reflux temperature, keeping refluxing for 20-30 minutes, cooling to 85-90 ℃, maintaining the temperature (85-90 ℃), dropwise adding ammonia water (6mL), continuously stirring for reaction for 1-1.5 hours, enabling the reaction solution to be in a black turbid state, naturally cooling to room temperature, standing for 0.5 hour, and adsorbing and separating by using a magnet to obtain a black solid; washing with distilled water for 3-5 times, vacuum drying at 60 deg.C for 12 hr to obtain black solid powder, i.e. magnetic Fe3O4Material (hereinafter referred to as product D); the distilled water used in this example was distilled water after ultrasonic treatment.
Example 5
200mL of distilled water was added with 0.4mmol of C70Fullerene, 0.4mmol of ferrous sulfate heptahydrate and 0.8mmol of anhydrous ferric chloride are introduced with nitrogen and stirred for 15 minutes, then heated to the reflux temperature, kept refluxing for 20-30 minutes, cooled to 85-90 ℃, kept at the temperature (85-90 ℃) and dropwise added with ammonia water (6mL), continuously stirred and reacted for 1-1.5 hours, the reaction solution is in a black turbid state, naturally cooled to the room temperature, kept standing for 0.5 hour, and then adsorbed and separated by a magnet to obtain a black solid; washing with distilled water for 3-5 times, vacuum drying at 60 deg.C for 12 hr to obtain black solid powder, i.e. magnetic C70A fullerene nano-material (hereinafter referred to as a product E); the distilled water used in this example was distilled water after ultrasonic treatment.
Example 6
200mL of distilled water was added with 0.1mmol of C70Fullerene, 0.4mmol of ferrous sulfate heptahydrate and 0.8mmol of anhydrous ferric chloride are introduced with nitrogen and stirred for 15 minutes, then heated to the reflux temperature, kept refluxing for 20-30 minutes, cooled to 85-90 ℃, kept at the temperature (85-90 ℃) and dropwise added with ammonia water (6mL), continuously stirred and reacted for 1-1.5 hours, the reaction solution is in a black turbid state, naturally cooled to the room temperature, kept standing for 0.5 hour, and then adsorbed and separated by a magnet to obtain a black solid; washing with distilled water for 3-5 times, vacuum drying at 60 deg.C for 12 hr to obtain black solid powder, i.e. magnetic C70Fullerene nano-material (withProduct F for short); the distilled water used in this example was distilled water after ultrasonic treatment.
EXAMPLE 7 plotting of Standard working curves
Reagent
The Annelliptin standard substance (content > 99.7%) and the tablet (specification: 100 mg/tablet) are provided by Jiangsu Union pharmaceutical industries, Inc.; methanol, ethanol, ammonia water, sodium acetate trihydrate and glacial acetic acid are purchased from the national medicine group. All water in the experiment is high-purity water, and the reagents are analytically pure.
Annelliptin standard solution (0.10 mg/mL): accurately weighing 0.010g of Annelliptin standard substance by using an analytical balance, dissolving the Annelliptin standard substance by using distilled water to a constant volume of 100mL, and storing the Annelliptin standard substance in a cool and dark place.
pH 3.0 buffer solution: 0.80g of sodium acetate trihydrate is weighed, dissolved in water, 5.4mL of glacial acetic acid are added, diluted to 500mL with water and the pH is adjusted to 3.0 on an acidimeter.
Instrument for measuring the position of a moving object
SHIMADZU UV-1780 spectrophotometer (UV-VIS spectrophotometer) (suzu, SHIMADZU instruments), centrifuge TDL80-2B (shanghai pavilion scientific instruments, inc); digital display constant temperature water bath (guo hua electric appliance limited); vacuum drying oven (shanghai-heng scientific instruments ltd); model DGG-9030B electric heating constant temperature air-blast drying oven (shanghai forest communication laboratory instruments ltd); pH S-25 type pH meter (Shanghai Jing Kelei Mag); a five-way KQ-50E ultrasonic cleaner.
Sample preparation
Preparation of anegliptin tablet-like: taking an Annelliptin tablet, grinding the Annelliptin tablet into powder, accurately weighing the powder which is equivalent to 1 tablet of medicine, adding the powder into a 100mL volumetric flask, adding 50mL of distilled water for ultrasonic dissolution, uniformly dispersing the tablet into turbid liquid after being completely dissolved, then using the distilled water for metering the volume to 100mL, filtering the turbid liquid by using a 0.45-micrometer filter membrane, taking the filtrate into a dry clean beaker, using a pipette for metering 5mL of the filtrate into another 50mL volumetric flask, using the distilled water for metering the volume, and shaking the solution uniformly.
Preparation of human serum samples: taking serum of healthy volunteers, adding a proper amount of Annelliptin standard solution, adding methanol according to the ratio of 1:4 to remove protein in the serum, centrifuging at 4000r/min for 15min, and taking supernatant for analysis.
Drawing of standard working curve
The absorbance values were plotted against the corresponding concentration of anegliptin (fig. 2), and the results of the measured analytical performance parameters are shown in table 1. As can be seen from Table 1, the linear range is 0.10-2.5. mu.g/mL, and the detection limit is 0.0926. mu.g/mL.
TABLE 1 Linear parameters and detection limits of analytical methods
Example 8
Example 1
(1) And (3) extraction: adding 1.0mL of pH 3.0 acetic acid-sodium acetate (HAc-NaAc) buffer solution, 20. mu.L of Annelliptin standard solution (0.10mg/mL) and 10mg of the product A prepared in example 1 into a 10.0mL centrifuge tube, diluting to 10mL with distilled water, shaking at room temperature for 10-15min, standing, and separating and extracting the adsorbent C by magnet adsorption70-Fe3O4After the upper layer solution is clear and transparent, taking the supernatant and detecting by using an ultraviolet-visible spectrophotometer, wherein the detection result is lower than the detection lower limit of a working curve, namely the Annelliptin is almost completely covered by C70-Fe3O4And (4) adsorbing.
(2) And (3) elution: the extraction adsorbent C obtained by the magnetic adsorption separation in the step (1)70-Fe3O4Placing in 5mL centrifuge tube, adding anhydrous ethanol, diluting to desired volume, shaking, oscillating at room temperature for 20-30min, standing, and separating with magnet to obtain C70-Fe3O4And (4) settling, taking the supernatant after the supernatant is clear and transparent, and detecting by using an ultraviolet-visible spectrophotometer, wherein the detection result is converted into 0.3931 mu g/mL (the theoretical value is 0.40 mu g/mL).
Example 2
(1) And (3) extraction: 1.0mL of pH 3.0 acetic acid-sodium acetate (HAc-NaAc) buffer solution, 20. mu.L of anegliptin standard solution (0.10mg/mL), and 20mg of the product B prepared in example 2 were added to a 10.0mL centrifuge tube, diluted to 10mL with distilled water, shaken well, and shaken at room temperatureSwinging for 10-15min, standing, and adsorbing with magnet to separate and extract adsorbent C70-Fe3O4After the upper layer solution is clear and transparent, taking the supernatant and detecting by using an ultraviolet-visible spectrophotometer, wherein the detection result is lower than the detection lower limit of a working curve, namely the Annelliptin is almost completely covered by C70-Fe3O4And (4) adsorbing.
(2) And (3) elution: the extraction adsorbent C obtained by the magnetic adsorption separation in the step (1)70-Fe3O4Placing in 5mL centrifuge tube, adding anhydrous ethanol, diluting to desired volume, shaking, oscillating at room temperature for 20-30min, standing, and separating with magnet to obtain C70-Fe3O4And (4) settling, taking the supernatant after the supernatant is clear and transparent, and detecting by using an ultraviolet-visible spectrophotometer, wherein the detection result is converted into 0.3929 mu g/mL (the theoretical value is 0.40 mu g/mL).
Example 3
And (3) extraction: 1.0mL of acetic acid-sodium acetate (HAc-NaAc) buffer solution with the pH value of 3.0, 20 mu L of anegliptin standard solution (0.10mg/mL) and 10mg of the product C prepared in the example 3 are respectively added into a 10.0mL centrifuge tube, the mixture is diluted to 10mL by distilled water, the mixture is shaken up, the mixture is shaken at room temperature for 10-15min, after the mixture is kept still, the magnet is used for adsorbing, separating and extracting the adsorbent, after the upper layer solution is clarified and transparent, the supernatant is taken and detected by an ultraviolet-visible spectrophotometer, and the detection result is converted into 0.1654 mu g/mL, which indicates that the product C has a general adsorption effect on the anegliptin and is not suitable for a solid phase extraction adsorbent in the anegliptin drug detection.
Example 4
And (3) extraction: 1.0mL of acetic acid-sodium acetate (HAc-NaAc) buffer solution with the pH value of 3.0, 20 mu L of anegliptin standard solution (0.10mg/mL) and 10mg of the product D prepared in the example 4 are respectively added into a 10.0mL centrifuge tube, the mixture is diluted to 10mL by distilled water, the mixture is shaken up, the mixture is shaken at room temperature for 10-15min, after the mixture is kept still, the magnet is used for adsorbing, separating and extracting the adsorbent, after the upper layer solution is clear and transparent, the supernatant is taken and detected by an ultraviolet-visible spectrophotometer, and the detection result is converted into 0.2218 mu g/mL, which indicates that the product D has a general adsorption effect on the anegliptin and is not suitable for a solid phase extraction adsorbent in the anegliptin drug detection.
Example 5
(1) And (3) extraction: 1.0mL of pH 3.0 acetic acid-sodium acetate (HAc-NaAc) buffer solution, 20. mu.L of anegliptin standard solution (0.10mg/mL) and 10mg of the product E prepared in example 5 were added to a 10.0mL centrifuge tube, diluted to 10mL with distilled water, shaken at room temperature for 10-15min, allowed to stand, and the adsorbent C was separated and extracted by magnet adsorption70-Fe3O4After the upper layer solution is clear and transparent, taking the supernatant and detecting by using an ultraviolet-visible spectrophotometer, wherein the detection result is lower than the detection lower limit of a working curve, namely the Annelliptin is almost completely covered by C70-Fe3O4And (4) adsorbing.
(2) And (3) elution: the extraction adsorbent C obtained by the magnetic adsorption separation in the step (1)70-Fe3O4Placing in 5mL volumetric flask, adding anhydrous ethanol, fixing volume, shaking, oscillating at room temperature for 20-30min, standing, and separating with magnet to obtain C70-Fe3O4And (4) settling, taking the supernatant after the supernatant is clear and transparent, and detecting by using an ultraviolet-visible spectrophotometer, wherein the detection result is converted into 0.3288 mu g/mL (the theoretical value is 0.40 mu g/mL). The product E has a good adsorption effect, but the elution and desorption effects are not ideal, so that the product E is not suitable for the solid phase extraction adsorbent in the drug detection of anergoid.
Example 6
(1) And (3) extraction: 1.0mL of pH 3.0 acetic acid-sodium acetate (HAc-NaAc) buffer solution, 20. mu.L of anegliptin standard solution (0.10mg/mL) and 10mg of the product F prepared in example 6 were added to a 10.0mL centrifuge tube, diluted to 10mL with distilled water, shaken at room temperature for 10-15min, allowed to stand, and the adsorbent C was separated and extracted by magnet adsorption70-Fe3O4And after the upper layer solution is clear and transparent, taking the supernatant and detecting the supernatant by using an ultraviolet-visible spectrophotometer, wherein the detection result is converted into 0.1258 mu g/mL, which indicates that the product F has an unsatisfactory adsorption effect on the anegliptin and is not suitable for a solid-phase extraction adsorbent in the anegliptin drug detection.
Example 9
The method utilizes the standard working curve of the concentration and the absorbance of the anegliptin prepared in the embodiment 7 and utilizes an ultraviolet-visible spectrophotometer to detect the precision and the reproducibility of the concentration of the anegliptin in the sample, and examine the accuracy and the recovery rate.
Precision and reproducibility
The method comprises the steps of respectively preparing two kinds of anegliptin standard solutions with the concentrations of 0.40 and 0.80 mu g/mL, continuously analyzing samples with the same concentration for 5 times in the same day with the precision in the same day, calculating the precision, and displaying that the RSD is 0.07-0.21% as a result, so that the method has good reproducibility and can be used for daily analysis.
In this experiment, the anegliptin tablet was measured by the working curve method, and the result was 101.5 mg/tablet, which was not significantly different from the labeled amount of 100 mg/tablet.
Accuracy and recovery
In the experiment, the recovery rate is measured by using a standard addition experiment method, and the accuracy of the method is evaluated. The relative recovery was calculated as follows:
in the formula Creal、Cadded、CfoundRespectively the concentration of the anergoid measured in the actual sample, the concentration of the anergoid standard solution added into the sample and the concentration of the anergoid measured in the sample after the standard substance is added. The results of the experimental measurements are shown in table 2. The recovery rate in the medicine is 96.8-102.3%, and the recovery rate in human serum is 96.8-100.9%, which indicates that the method has better accuracy and can be used for measuring the content of the anegliptin in the medicine.
TABLE 2 recovery rate experiment
Therefore, the method for detecting the concentration of the anegliptin in the sample by using the ultraviolet-visible spectrophotometer has high precision and good reproducibility, and the detection result in the embodiment 8 is credible.
Claims (4)
1. Magnetic C70The application of the fullerene nano-material in the drug detection of the Annelliptin is characterized in that the magnetic C70The preparation method of the fullerene nano-material comprises the following steps:
(1) taking a proper amount of distilled water, adding C70Introducing nitrogen or argon into fullerene, ferrous sulfate heptahydrate and anhydrous ferric chloride, stirring for 15-20 minutes, heating to a reflux temperature, keeping refluxing for 20-30 minutes, cooling to 85-90 ℃, maintaining the temperature of 85-90 ℃, dropwise adding ammonia water, continuously stirring for reaction for 1-1.5 hours, enabling the reaction liquid to be in a black turbid state, naturally cooling to room temperature, standing for 0.5 hour, and then adsorbing and separating by using a magnet to obtain a black solid;
(2) washing the black solid obtained in the step (1) with distilled water for 3-5 times, and vacuum drying at 60 ℃ for 12-24h to obtain black solid powder, namely magnetic C70A fullerene nanomaterial; distilled water and C in the step (1)70The dosage of fullerene, ferrous sulfate heptahydrate, anhydrous ferric chloride and ammonia water is 0.1mmol C per 100mL distilled water70Fullerene, 0.2mmol ferrous sulfate heptahydrate, 0.4mmol anhydrous ferric chloride and 3-5mL ammonia water; the distilled water is selected from distilled water after ultrasonic treatment.
2. The use as claimed in claim 1, characterized in that the magnetic C is70The fullerene nano-material plays a role as a solid phase extraction adsorbent.
3. The use as claimed in claim 2, characterized in that the magnetic C is70Application of fullerene nano-material in preparation of solid-phase extraction adsorbent for detecting Annelliptin drugs.
4. The use according to claim 1, characterized in that it comprises the following steps:
(1) and (3) extraction: respectively adding 1.0mL of pH 3.0 acetic acid-sodium acetate buffer solution, a proper amount of sample solution to be detected and 10-20mg of magnetic C into a 10.0mL centrifuge tube70Diluting fullerene nanometer material with distilled water to 10mL, shaking up, oscillating at room temperature for 10-15min,after standing still, magnetic C is separated by magnet adsorption70The fullerene nano material is used for taking supernatant fluid to be detected by an ultraviolet-visible spectrophotometer after the supernatant fluid is clear and transparent;
(2) and (3) elution: magnetic C obtained by adsorbing and separating the magnetic C obtained in the step (1) by using a magnet70Placing fullerene nano material in a centrifuge tube, adding anhydrous ethanol, fixing volume, shaking, oscillating at room temperature for 20-30min, standing, and separating with magnet to obtain magnetic C70And (3) settling the fullerene nano material, and taking supernatant fluid to detect by using an ultraviolet-visible spectrophotometer after the supernatant fluid is clear and transparent.
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| CN104785197A (en) * | 2014-01-16 | 2015-07-22 | 中国药科大学 | Preparation method of mixed hemi-micelle solid phase extractant based on Fe3O4 magnetic nanoparticles |
| CN105854796A (en) * | 2016-04-08 | 2016-08-17 | 济南大学 | Preparation method and application of magnetic bimetallic oxide/carbon composite material |
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| CN104258807A (en) * | 2014-10-13 | 2015-01-07 | 中国环境科学研究院 | Magnetic nano material solid phase extracting agent as well as preparation method and application thereof |
| CN105854796A (en) * | 2016-04-08 | 2016-08-17 | 济南大学 | Preparation method and application of magnetic bimetallic oxide/carbon composite material |
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