CN113866092A - Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS (surface enhanced Raman scattering) - Google Patents

Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS (surface enhanced Raman scattering) Download PDF

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CN113866092A
CN113866092A CN202111129678.6A CN202111129678A CN113866092A CN 113866092 A CN113866092 A CN 113866092A CN 202111129678 A CN202111129678 A CN 202111129678A CN 113866092 A CN113866092 A CN 113866092A
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hollow fiber
fiber membrane
eggs
antibiotics
tube
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CN113866092B (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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  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention belongs to the field of food safety detection, and relates to a controllable extraction and detection integrated device for 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 firstly treated by a first extracting agent in an ultrasonic mode, so that tiny gaps on the tube wall of the hollow fiber membrane tube are fully filled with the first extracting agent, then a second extracting agent is absorbed into a cavity of the hollow fiber membrane tube, and then the hollow fiber membrane tube is sealed by a sealing cover with the bottom modified with silver. And after the completely sealed hollow fiber membrane is inserted into egg liquid and stirred and extracted, the handle is pressed down to push the knob, so that the second extracting agent in the hollow fiber cavity is pushed into the sealing cover, and the antibiotics in the eggs can be rapidly detected through a Raman spectrometer after the sealing cover is separated.

Description

Integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS (surface enhanced Raman scattering)
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 (surface enhanced Raman scattering).
Background
Antibiotics are widely used in the breeding industry as drugs for preventing and treating infectious diseases and promoting growth, and the antibiotics are commonly used in the following fields: quinolones and sulfonamides, etc., including sulfamethazine, enrofloxacin, norfloxacin, ofloxacin, ciprofloxacin. With the wide application of antibiotics in the breeding industry, the antibiotics are likely to remain in eggs, and the residual antibiotics in the egg products can pose health threats to consumers. Although the conventional chromatography-mass spectrometry tandem technology for detecting the antibiotics in the eggs has high sensitivity, the operation is complicated and long-time consuming, a large amount of pretreatment waste liquid is generated, and the method is not suitable for rapid analysis and detection of a large amount of samples. Therefore, the invention is very necessary to invent an integrated device for rapidly detecting the antibiotics in the eggs.
Liquid-liquid extraction is an important separation technique that utilizes the property of a solute to separate or purify substances by transferring the compound from one solvent to another, i.e., by utilizing the property of a difference in solubility or partition coefficient between two partially miscible liquid phases. 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 the like, and extracts antibiotic molecules into the inner cavity of the hollow fiber membrane.
Disclosure of Invention
The invention aims to design an extraction and detection integrated device for rapidly detecting antibiotics in eggs, which aims to solve the problem that the detection of the antibiotics in the eggs is complicated at present, and realizes the integration of the rapid extraction and detection process of the antibiotics in the eggs by combining the extraction process with the detection process, combining a hollow fiber membrane with an SERS (surface enhanced Raman spectroscopy) technology and combining liquid-liquid microextraction with the SERS technology without complicated sample pretreatment.
The technical scheme of the invention is as follows:
the hollow fiber membrane extraction and SERS combined extraction and detection integrated device for the antibiotics in the eggs 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 tube structures with openings at two ends.
The two ends of the connector 3 are respectively connected with one end of the connecting outer pipe 2 and one end of the hollow fiber membrane pipe 4, and the center of the connector 3 is provided with a through hole so that the outer pipe 2 is communicated with the hollow fiber membrane pipe 4.
The push button 1 is of a piston structure, the inner end of the push button is positioned inside the outer tube 2, the outer end of the push button is positioned outside the outer tube 2, and the inner end of the push button 1 can move along the inner wall of the outer tube 2 by pushing the outer end of the push button 1.
The hollow fiber membrane tube 4 is firstly subjected to ultrasonic treatment by a first extracting agent, so that gaps of the hollow fiber membrane are fully filled by the first extracting agent, then a second extracting agent is added into a 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 in use, the integrated device is moved downwards, the probe is inserted into egg liquid, stirred and extracted with antibiotics, and then moved upwards to separate the probe from the egg liquid; move down and loosen sealed lid 5, promote downwards and push away and turn round 1, make the second extractant that contains the antibiotic in the 4 lumens of hollow fiber membrane tube drop to sealed lid 5 in, then detect the liquid of waiting to detect in sealed lid 5 through raman spectroscopy to the realization is to the antibiotic in the egg and carry out short-term test.
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 device combines the extraction and detection processes into one device, can be directly inserted into egg liquid for extraction, and can directly detect by means of an SERS technology. The egg is not required to be subjected to complex sample pretreatment, so that 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 integrated device disclosed by the invention is simple in structure under normal pressure in a working state, strong in adaptability, convenient to operate, safe, reliable and convenient to maintain.
3. The integrated device can be recycled and is environment-friendly.
4. The integrated device provided by the invention has obvious 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 integrated process of extraction and detection.
FIG. 3 is a graph of SERS signals detected by the rapid extraction of the antibiotic mixed system in eggs in the example.
In the figure: 1 push button, 2 outer tube, 3 connector, 4 hollow fiber membrane tube, 5 sealing cover.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
The invention discloses an integrated device for extracting and detecting antibiotics in eggs by combining hollow fiber membrane extraction with SERS (surface enhanced Raman scattering), which comprises a push-button 1, an outer tube 2, a connector 3, a hollow fiber membrane tube 4 and a sealing cover 5 as shown in figure 1.
In the extraction process, the micro gaps on the pipe wall of the hollow fiber membrane pipe 4 are utilized to isolate macromolecules and simultaneously extract target micromolecules (antibiotic molecules) to the cavity. Then the extract liquor in the cavity is collected into a sealing cover for SERS detection, so that the extraction and detection of the antibiotics in the eggs are integrated.
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, so that the wall hole of the hollow fiber membrane tube 4 is filled with the first extractant, and completely removing the tributyl phosphate in the cavity of the hollow fiber membrane tube 4 by using a push-twist 1. Then the hollow fiber membrane tube 4 is inserted into a second extractant (hydrochloric acid aqueous solution), and the push button 1 is pulled out upwards to fill the hollow cavity of the hollow fiber membrane tube 4 with the hydrochloric acid aqueous solution. Sealing the sealing cover 5 to the bottom end of the hollow fiber membrane tube 4, inserting the hollow fiber membrane tube into the egg liquid to be detected, stirring and extracting, enriching antibiotic molecules in the egg liquid into the first extractant, and performing back extraction on the antibiotic molecules in the first extractant by using the second extractant. And finally, loosening the sealing cover 5, pushing the push button 1 downwards, and pushing a second extracting agent containing antibiotics in the hollow fiber membrane tube 4 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 of the sealing cover is made of Polydimethylsiloxane (PDMS), and a layer of nano silver film is plated on the surface of the monocrystalline silicon and is used as an SERS enhanced substrate; the hollow fiber membrane tube 4 is made of polypropylene, the inner diameter is 600 microns, and the thickness of the tube wall is 200 microns; the ultrasonic extraction time of the hollow fiber membrane tube 4 in tributyl phosphate is 30 minutes, the optimal concentration of 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: the wavelength of exciting light is 785nm, the laser power is 1%, the integration time is 10s, a 50-time long-focus lens is adopted, the size of a light spot is 1um, and the average times are 3 times.
In order to test the effectiveness of the device, the device is adopted to detect a 100mg/kg-100ug/kg norfloxacin, enrofloxacin, ciprofloxacin, ofloxacin and sulfamethazine antibiotic mixed system in eggs. SERS results are shown in FIG. 3, norfloxacin, enrofloxacin and ciprofloxacin 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-1Has obvious characteristic peak, and the ofloxacin is at 889cm-1Has obvious characteristic peak, and the sulfadimidine is at 633cm-1，1004cm-1，1079cm-1，1147cm-1，1183cm-1，1592cm-1The characteristic peak is obvious and has good effect. Therefore, the invention can be used for eggsThe antibiotic in (1) is extracted and detected quickly.

Claims (4)

1. The device is characterized in that the integrated device 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 pipe (2) and the hollow fiber membrane pipe (4) are of pipe body structures with openings at two ends;
the two ends of the connector (3) are respectively connected with the connecting outer pipe (2) and one end of the hollow fiber membrane pipe (4), and a through hole is formed in the center of the connector (3) so that the outer pipe (2) is communicated with the hollow fiber membrane pipe (4);
the push button (1) is of a piston structure, the inner end of the push button is positioned inside the outer pipe (2), the outer end of the push button is positioned outside the outer pipe (2), and the outer end of the push button (1) can enable the inner end of the push button (1) to move along the inner wall of the outer pipe (2);
the hollow fiber membrane tube (4) is firstly subjected to ultrasonic treatment by a first extracting agent, so that gaps of the hollow fiber membrane are fully filled with the first extracting agent, then a second extracting agent is absorbed into a tube cavity, and then 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 of the sealing cover is made of Polydimethylsiloxane (PDMS), and a layer of nano silver film is plated on the surface of the monocrystalline silicon;
when in use, the integrated device is moved downwards, the probe is inserted into egg liquid, stirred and extracted with antibiotics, and then moved upwards to separate the probe from the egg liquid; move down and loosen sealed lid (5), promote downwards and push away and turn round (1), make the second extractant that contains the antibiotic in hollow fiber membrane pipe (4) lumen drop to sealed lid (5) in, then detect the liquid of waiting to detect in sealed lid (5) through raman spectroscopy to the realization is to the antibiotic in the egg and is carried out the short-term test.
2. The device integrating hollow fiber membrane extraction and SERS (surface enhanced Raman Scattering) for extracting and detecting antibiotics in eggs, according to claim 1, is characterized in that the hollow fiber membrane tube (4) is made of polypropylene.
3. The device for integrating extraction and detection of antibiotics in eggs by combining hollow fiber membrane extraction with SERS (surface enhanced Raman scattering) according to claim 1 or 2, wherein the first extracting agent is tributyl phosphate; the second extractant is hydrochloric acid aqueous solution.
4. The device for integrating extraction and detection of antibiotics in eggs by hollow fiber membrane extraction and SERS (surface enhanced Raman scattering) according to claim 3, wherein the concentration of the hydrochloric acid aqueous solution is 0.1M/L.
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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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HUI XU ET AL.: "Residue analysis of tetracyclines in milk by HPLC coupled with hollow fiber membranes-based dynamic liquid-liquid micro-extraction", FOOD CHEMISTRY, vol. 232, pages 198 - 202, XP085001567, DOI: 10.1016/j.foodchem.2017.04.021 *
曹丁丁 等: "食品中四环素残留检测方法比较分析", 生物加工过程, vol. 18, no. 05, pages 636 - 641 *
林珊珊 等: "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", 分析化学, vol. 41, no. 10, pages 1511 - 1517 *

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