CN113866092B - Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS - Google Patents

Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS Download PDF

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CN113866092B
CN113866092B CN202111129678.6A CN202111129678A CN113866092B CN 113866092 B CN113866092 B CN 113866092B CN 202111129678 A CN202111129678 A CN 202111129678A CN 113866092 B CN113866092 B CN 113866092B
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hollow fiber
fiber membrane
tube
eggs
extractant
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CN113866092A (en
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单佳佳
任涛
靳梦轲
李欣静
王晶
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Dalian University of Technology
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Dalian University of Technology
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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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention belongs to the field of food safety detection, and relates to a controllable integrated device for extracting and detecting antibiotics in eggs, which mainly comprises a handle and a probe, wherein the handle consists of a push button, an outer tube and a connector; the probe comprises a hollow fiber membrane tube and a sealing cover. The hollow fiber membrane tube is first treated with the first extractant ultrasonically to fill the micro gaps in the wall of the hollow fiber membrane tube with the first extractant, and then the second extractant is sucked into the cavity of the hollow fiber membrane tube and then sealed with the sealing cover with silver modified at the bottom. After the fully sealed hollow fiber membrane is inserted into egg liquid for stirring and extraction, the handle is pressed down to push the knob, so that the second extractant in the hollow fiber cavity is pushed into the sealing cover, and the sealing cover is separated to rapidly detect antibiotics in eggs through the Raman spectrometer.

Description

Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS
Technical Field
The invention belongs to the field of food safety detection, and relates to an integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS.
Background
Antibiotics are widely used in the aquaculture industry as medicines for preventing and treating infectious diseases, and the common ones are: quinolones and sulfonamides, including sulfadimidine, enrofloxacin, norfloxacin, ofloxacin, ciprofloxacin, and the like. With the widespread use of antibiotics in the farming industry, there is a high probability that they remain in eggs, which can pose a health threat to consumers. The common chromatographic-mass spectrometry tandem technology for detecting antibiotics in eggs has high sensitivity, but is complex in operation and long in time consumption, generates a large amount of pretreatment waste liquid, and is not suitable for rapid analysis and detection of a large number of samples. Therefore, it is necessary to invent an integrated device for rapidly detecting antibiotics in eggs.
Liquid-liquid extraction is an important separation technique that exploits the property of a solute that differs in solubility or partition coefficient between two partially miscible liquid phases to effect separation or purification of a substance, i.e., the transfer of a compound from one solvent to another. Has the characteristics of good separation effect, high selectivity, strong adaptability and the like. The hollow fiber membrane can isolate macromolecules such as lipid and extract antibiotic molecules into the inner cavity of the hollow fiber membrane.
Disclosure of Invention
Aiming at the current situation that the detection of antibiotics in eggs is complicated, the invention aims to design an extraction and detection integrated device for rapidly detecting the antibiotics in eggs, complex sample pretreatment is not needed, the extraction process and the detection process are combined, the hollow fiber membrane and the SERS technology are combined, and the device combining the liquid-liquid microextraction and the Surface Enhanced Raman Spectroscopy (SERS) technology is used for realizing the integration of the rapid extraction and detection process of the antibiotics in eggs.
The technical scheme of the invention is as follows:
the integrated device for extracting and detecting the antibiotics in the eggs by combining the hollow fiber membrane extraction with the SERS comprises a handle and a probe; the handle comprises a push button 1, an outer tube 2 and a connector 3; the probe comprises a hollow fiber membrane tube 4 and a sealing cover 5.
The outer tube 2 and the hollow fiber membrane tube 4 are of tube body structures with two open ends.
The two ends of the connector 3 are respectively connected with one end of the connecting outer tube 2 and one end of the hollow fiber membrane tube 4, and a through hole is arranged in the center of the connector 3, so that the outer tube 2 and the hollow fiber membrane tube 4 are communicated.
The push button 1 is of a piston structure, the inner side end of the push button 1 is positioned inside the outer tube 2, the outer side end of the push button is positioned outside the outer tube 2, and the inner side end of the push button 1 can move along the inner wall of the outer tube 2 by pushing the outer side end of the push button 1.
The hollow fiber membrane tube 4 is firstly subjected to ultrasonic treatment by a first extractant, so that the gaps of the hollow fiber membrane are fully filled by the first extractant, then a second extractant is added into the tube cavity, and then the sealing cover 5 is arranged at the tail end of the hollow fiber membrane tube 4 for sealing.
The bottom of the sealing cover 5 is made of monocrystalline silicon, the side wall is made of Polydimethylsiloxane (PDMS), and a layer of nano silver film is plated on the surface of the monocrystalline silicon.
When the device is used, the integrated device is moved downwards, the probe is inserted into the egg liquid for stirring and extracting antibiotics, and then the integrated device is moved upwards, so that the probe is separated from the egg liquid; the sealing cover 5 is moved downwards to loosen, the pushing button 1 is pushed downwards, so that a second extractant containing antibiotics in the tube cavity of the hollow fiber membrane tube 4 falls into the sealing cover 5, and then the liquid to be detected in the sealing cover 5 is detected by a Raman spectrometer, so that the antibiotics in eggs are rapidly detected.
The hollow fiber membrane tube 4 is made of polypropylene.
The first extractant is tributyl phosphate.
The second extractant is hydrochloric acid aqueous solution, and the concentration is preferably 0.1M/L.
The invention has the beneficial effects that:
1. compared with the traditional detection method, the integrated device has high flexibility, and the device synthesizes the extraction and detection processes into one device, can be directly inserted into egg liquid for extraction, and can be directly detected by means of SERS technology. The complex sample pretreatment of eggs is not needed, the use of organic reagents is reduced, the detection time is shortened, the detection efficiency is improved, and the environmental pressure is relieved.
2. The working state of the integrated device is normal pressure, the structure is simple, the adaptability is strong, the operation is convenient, the safety and the reliability are realized, and the maintenance is convenient.
3. The integrated device provided by the invention can be recycled and is environment-friendly.
4. The integrated device has remarkable extraction and enhancement effects on quinolones, sulfonamides and the like in eggs.
Drawings
Fig. 1 is a schematic structural diagram of an integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS.
Fig. 2 is a schematic diagram of an extraction and detection integrated process.
Fig. 3 is a graph of SERS signals from a rapid extraction test of an antibiotic cocktail in eggs in an example.
In the figure: 1 push button, 2 outer tube, 3 connector, 4 hollow fiber membrane tube, 5 sealing cover.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
The invention relates to an integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS, which is shown in figure 1 and comprises a push button 1, an outer tube 2, a connector 3, a hollow fiber membrane tube 4 and a sealing cover 5.
In the extraction process, small gaps on the wall of the hollow fiber membrane tube 4 are utilized to isolate macromolecules and extract target small molecules (antibiotic molecules) into the cavity. And then collecting the extract liquid in the cavity into a sealing cover for SERS detection, so as to realize the extraction and detection integration of antibiotics in eggs.
In this embodiment, the specific use process is as follows (as shown in fig. 2):
firstly, immersing the hollow fiber membrane tube 4 into a first extractant (tributyl phosphate) for ultrasonic treatment, filling the wall holes of the hollow fiber membrane tube 4 with the first extractant, and completely removing the tributyl phosphate in the hollow cavity of the hollow fiber membrane tube 4 by using the push button 1. Then, the hollow fiber membrane tube 4 is inserted into the second extractant (hydrochloric acid aqueous solution), and the push knob 1 is pulled upward to fill the hollow fiber membrane tube 4 with the hydrochloric acid aqueous solution. And then sealing the sealing cover 5 to the bottom end of the hollow fiber membrane tube 4, inserting the sealing cover into egg liquid to be tested, stirring and extracting, enriching antibiotic molecules in the egg liquid into a first extractant, and performing back extraction on the antibiotic molecules in the first extractant by a second extractant. Finally, the sealing cover 5 is loosened, the pushing knob 1 is pushed downwards, and the second extractant containing antibiotics in the hollow fiber membrane tube 4 is pushed into the sealing cover 5 to directly carry out SERS detection.
The bottom of the sealing cover 5 is made of monocrystalline silicon, the side wall is made of Polydimethylsiloxane (PDMS), and a layer of nano silver film is plated on the surface of the monocrystalline silicon and used as a SERS reinforced substrate; the hollow fiber membrane tube 4 is made of polypropylene, the inner diameter is 600 microns, and the tube wall thickness is 200 microns; the ultrasonic extraction time of the hollow fiber membrane tube 4 in tributyl phosphate is 30 minutes, the optimal concentration of the hydrochloric acid aqueous solution is 0.1M/L, and the extraction time in egg liquid is 1 hour. The most suitable parameters for SERS detection are: excitation light wavelength 785nm, laser power 1%, integration time 10s,50 times of long focal lens, spot size 1um, average number of times 3.
In order to test the effectiveness of the device, 100mg/kg-100ug/kg of norfloxacin, enrofloxacin, ciprofloxacin, ofloxacin and sulfadimidine antibiotics mixed system in eggs are detected by adopting the device. The SERS result is shown in FIG. 3, in which norfloxacin, enrofloxacin and ciprofloxacin are present at 665cm -1 ，703cm -1 ，751cm -1 ，793cm -1 ，829cm -1 ，851cm -1 ，1224cm -1 ，1254cm -1 ，1302cm -1 ，1342cm -1 ，1396cm -1 ，1456cm -1 ，1493cm -1 ，1511cm -1 ，1629cm -1 The characteristic peak is obvious, and ofloxacin is 889cm -1 The characteristic peak is obvious, and sulfadimidine is found in 633cm -1 ，1004cm -1 ，1079cm -1 ，1147cm -1 ，1183cm -1 ，1592cm -1 The characteristic peaks are obvious, and the effect is good. Therefore, the invention can rapidly extract and detect the antibiotics in the eggs.

Claims (4)

1. The integrated device for extracting and detecting the antibiotics in the eggs by combining the hollow fiber membrane extraction with the SERS is characterized by comprising a handle and a probe; the handle comprises a push button (1), an outer tube (2) and a connector (3); the probe comprises a hollow fiber membrane tube (4) and a sealing cover (5);
the outer tube (2) and the hollow fiber membrane tube (4) are tube structures with two open ends;
the two ends of the connector (3) are respectively connected with one end of the connecting outer tube (2) and one end of the hollow fiber membrane tube (4), and a through hole is formed in the center of the connector (3) so that the outer tube (2) is communicated with the hollow fiber membrane tube (4);
the push button (1) is of a piston structure, the inner side end of the push button is positioned inside the outer tube (2), the outer side end of the push button is positioned outside the outer tube (2), and the inner side end of the push button (1) can move along the inner wall of the outer tube (2) by pushing the outer side end of the push button (1);
the hollow fiber membrane tube (4) is subjected to ultrasonic treatment by a first extractant, so that the gaps of the hollow fiber membrane are fully filled with the first extractant, then a second extractant is sucked into the tube cavity, and a sealing cover (5) is arranged at the tail end of the hollow fiber membrane tube (4) for sealing;
the bottom of the sealing cover (5) is made of monocrystalline silicon, the side wall is made of Polydimethylsiloxane (PDMS), and a layer of nano silver film is plated on the surface of the monocrystalline silicon;
when the device is used, the integrated device is moved downwards, the probe is inserted into the egg liquid for stirring and extracting antibiotics, and then the integrated device is moved upwards, so that the probe is separated from the egg liquid; the sealing cover (5) is moved downwards to loosen, the pushing button (1) is pushed downwards, so that a second extractant containing antibiotics in the tube cavity of the hollow fiber membrane tube (4) falls into the sealing cover (5), and then the liquid to be detected in the sealing cover (5) is detected through a Raman spectrometer, so that the antibiotics in eggs are rapidly detected.
2. The integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS as claimed in claim 1, wherein the hollow fiber membrane tube (4) is made of polypropylene.
3. The integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS according to claim 1 or 2, wherein the first extractant is tributyl phosphate; the second extractant is hydrochloric acid aqueous solution.
4. The integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS according to claim 3, wherein the concentration of the hydrochloric acid aqueous solution is 0.1M/L.
CN202111129678.6A 2021-09-26 2021-09-26 Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS Active CN113866092B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691206A (en) * 1990-04-02 1997-11-25 Pawliszyn; Janusz B. Method and device for solid phase microextraction and desorption
CN101637668A (en) * 2009-01-14 2010-02-03 中山大学 Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof
CN104458698A (en) * 2014-12-09 2015-03-25 山东大学 Method for detecting organic pollutants by virtue of combination of solid phase micro-extraction and surface enhancement Raman
CN209645896U (en) * 2019-01-22 2019-11-19 四川海润检测有限公司 A kind of solid-liquid micro-extraction device
CN112697765A (en) * 2020-11-11 2021-04-23 上海应用技术大学 Portable storage type surface enhanced Raman sensor, and preparation method, detection method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691206A (en) * 1990-04-02 1997-11-25 Pawliszyn; Janusz B. Method and device for solid phase microextraction and desorption
CN101637668A (en) * 2009-01-14 2010-02-03 中山大学 Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof
CN104458698A (en) * 2014-12-09 2015-03-25 山东大学 Method for detecting organic pollutants by virtue of combination of solid phase micro-extraction and surface enhancement Raman
CN209645896U (en) * 2019-01-22 2019-11-19 四川海润检测有限公司 A kind of solid-liquid micro-extraction device
CN112697765A (en) * 2020-11-11 2021-04-23 上海应用技术大学 Portable storage type surface enhanced Raman sensor, and preparation method, detection method and application thereof

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Title
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微波辅助中空纤维液相微萃取-液相色谱-串联质谱法同时快速测定牛奶中27种抗生素残留;林珊珊 等;分析化学;41(10);第1511-1517页 *
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