CN116296728A - A dry method for extracting medicine from hair - Google Patents

Abstract

The invention discloses a method for extracting medicines from hair by a dry method, which comprises the following steps: obtaining a hair sample; adding magnetic solid phase extraction microspheres into a hair sample for first grinding to obtain a first mixture; adding a cosolvent into the mixture for second grinding to obtain a second mixture; separating the hair and the magnetic solid phase extraction microsphere in the second mixture by using a magnetic attraction mode to obtain the magnetic solid phase extraction microsphere adsorbed with the medicine; the addition amount of the magnetic solid phase extraction microsphere is 1/100-1/10 of the weight of the hair, and the dry extraction method changes the traditional mode of wet extraction of the medicine in the hair by using a large amount of solution, saves a large amount of extraction solvent, simplifies operation steps and improves extraction efficiency.

Description

A dry method for extracting medicine from hair

technical field

The invention relates to the technical field of extracting medicine from hair, in particular to a method for extracting medicine from hair by dry method.

Background technique

Hair is a commonly used sample in animal and human illicit drug monitoring. At present, the method of wet extraction is used for the detection of prohibited drugs in hair. The conventional operation steps are: first grind the hair into debris, then add extraction solvent to the hair debris, so that the drug is transferred from the hair debris to the extraction solvent, and then use different purification materials to purify the drug in the extraction solvent. Purification and enrichment, and finally, different detection methods are used to detect the drug concentration.

The invention patent with application number CN202210978031.9 discloses a method for detecting common drugs in hair, including the following steps: S1: hair sample collection; S2: hair sample processing: mixing hair sample, hair lysate and zirconia grinding beads Grinding to obtain a mixture; S3: hair sample detection.

The invention patent with the application number CN201810272590.1 discloses a method for quantitative detection of barbiturates in hair, which includes the following steps: step a, cleaning the hair sample to obtain a sample to be tested; The sample to be tested is ground with liquid nitrogen to obtain a pulverized sample, and the pulverized sample is subjected to ultrasonic extraction with methanol to obtain a solution to be tested; step c, using a high-resolution liquid chromatography/mass spectrometry analysis method to analyze the solution to be tested in step b The detection is carried out to obtain the detection data of the high-resolution liquid chromatography/mass spectrometry of the barbiturates in the hair, and the content of the barbiturates in the hair is calculated.

In summary, the existing technical methods have obvious defects in practical application, mainly including: ①Under the conventional grinding method, the hair fragmentation takes time and labor, and the degree of fragmentation is difficult to control, resulting in insufficient drug exposure in the hair. Uniform, large detection error; ②Due to the low density and imbibition of hair debris, a large amount of extraction solvent is required for hair extraction; ③It is difficult to separate hair debris from the extraction solvent. Usually, after centrifugation, the hair debris can quickly The resuspension in the extraction solvent seriously interferes with the subsequent purification operation.

Contents of the invention

The object of the present invention is to provide a method for dry extraction of drugs in hair, by adding magnetic solid-phase extraction microspheres and a small amount of co-solvent to the hair sample, grinding and mixing, so that the drug in the hair is in the co-solvent "bond bridge" and Under the action of the functional groups on the surface of the magnetic solid phase extraction microspheres, the surface functional groups are transferred and adsorbed into the pores on the surface of the magnetic solid phase extraction microspheres to realize the separation from the hair, which changes the traditional way of using a large amount of solution to wet extract the drug in the hair, saving a lot of time The extraction solvent simplifies the operation steps and improves the extraction efficiency.

The present invention is realized through the following technical solutions:

A dry method for extracting medicine from hair, comprising:

obtain hair samples;

adding magnetic solid-phase extraction microspheres to the hair sample for first grinding to obtain a first mixture;

adding co-solvent to the mixture for second grinding to obtain a second mixture;

separating the hair and the magnetic solid-phase extraction microspheres in the second mixture by magnetic attraction to obtain the magnetic solid-phase extraction microspheres adsorbed with the drug;

Wherein, the added amount of the magnetic solid-phase extraction microspheres is 1/100-1/10 of the hair weight.

Preferably, the obtaining the hair sample includes: collecting hair, and obtaining the hair sample after decontamination and drying.

Preferably, said hair is selected from humans or animals.

Preferably, the decontamination treatment includes descaling and degreasing the hair with a rinsing solution.

Preferably, the rinsing solution is one or more of clear water, sodium dodecylsulfonate solution, dilute hydrochloric acid solution or methanol solution.

Preferably, the drying treatment includes drying in an oven, and the drying temperature is controlled at 50-70°C.

Preferably, the drying treatment includes natural volatilization drying or drying with filter paper.

Preferably, the grinding is carried out with a mortar or a special hair grinder.

Preferably, the magnetic solid-phase extraction microspheres have a porous core-shell structure with a diameter of 0.1-10 μm.

Preferably, the core layer of the porous core-shell structure is magnetic ferric iron tetroxide, and the shell layer is porous particles of silica modified with active functional groups.

Preferably, the co-solvent comprises a mixture of an organic solvent and a volatile acid or a volatile base.

Preferably, the number of times of adding the co-solvent is several times, and the time of the second grinding is 1-2 minutes.

Preferably, the added amount of the solubilizer is enough to wet the hair.

Preferably, before separating the hair and the magnetic solid-phase extraction microspheres in the second mixture by means of magnetic attraction, it also includes completely volatilizing the co-solvent.

As a preference, the separation of hair and magnetic solid-phase extraction microspheres in the second mixture by means of magnetic attraction to obtain magnetic solid-phase extraction microspheres adsorbed with drugs includes:

Transfer the second mixture to a centrifuge tube, make the magnet close to the wall of the centrifuge tube, and shake to separate the magnetic solid-phase extraction microspheres from the hair;

Turn the centrifuge tube upside down and pour out the hair to obtain the magnetic solid-phase extraction microspheres adsorbed with the drug.

Preferably, after obtaining the magnetic solid-phase extraction microspheres adsorbed with drugs, it also includes performing purification treatment on the magnetic solid-phase extraction microspheres.

Preferably, the purification process includes using a solvent to remove impurities, elute, dry and redissolve the magnetic solid phase extraction microspheres to obtain the sample to be tested.

In summary, the extraction of drugs from hair is usually done by adding extraction solution to the ground hair debris, but the density of hair debris is small and imbibition, so a large amount of extraction solution is consumed; hair debris is easy to agglomerate in the extraction solution The clusters float on the surface of the liquid, resulting in insufficient extraction and low efficiency; it is difficult to completely separate the hair debris from the extraction solution, which affects the subsequent steps of purification and enrichment. And the present invention provides a kind of method of extracting the medicine in hair by dry method, mix and grind by hair and magnetic solid-phase extraction microsphere, the shearing force that the hard sphere of magnetic solid-phase extraction microsphere produces in grinding process can make hair Quickly break and break, and add co-solvent to make the drug in the hair adsorb to the magnetic solid-phase extraction microspheres, and then transfer the mixture of hair and magnetic solid-phase extraction microspheres to a centrifuge tube, and a magnetic field is applied to the outside of the centrifuge tube. Frequency vibration centrifuge tube, the magnetic solid phase extraction microspheres adsorbed with drugs are attracted to the magnet under the action of the magnetic field and separated from the hair, so as to achieve the purpose of dry extraction of drug residues in hair and effectively solve the problem of conventional wet extraction of drugs in hair Existing defects.

Description of drawings

Fig. 1 is a schematic flow chart of a method for extracting medicine from hair by dry method.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the implementation of the present application example, not all examples. Based on the embodiments in the present application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present application.

According to a typical implementation of the present invention, there is provided a method for extracting medicine in hair by dry method, as shown in Figure 1, the method includes:

obtain hair samples;

adding magnetic solid-phase extraction microspheres to the hair sample for first grinding to obtain a first mixture;

adding co-solvent to the mixture for second grinding to obtain a second mixture;

separating the hair and the magnetic solid-phase extraction microspheres in the second mixture by magnetic attraction to obtain the magnetic solid-phase extraction microspheres adsorbed with the drug;

Wherein, the added amount of the magnetic solid-phase extraction microspheres is 1/100-1/10 of the hair weight.

Hair grinding generally uses grinding rods or grinding balls to directly grind the hair. Because the hair is soft and has strong toughness, it usually takes a long time to destroy the inherent structure of the hair and grind the hair into debris, and the hair obtained by grinding The debris is very uneven; the present invention adds magnetic solid-phase extraction microspheres when the hair is ground, and the magnetic solid-phase extraction microspheres have a uniform and moderate shape and volume, and the surface is hard and porous, and is attached to the hair surface after mixing with the hair. When grinding, it can generate a strong shearing force on the hair and act as a grinding aid to increase the hair grinding efficiency by 2 to 5 times, and the hair is fully broken, and the obtained hair debris is small in size and uniform.

As an optional embodiment, the obtaining the hair sample includes: collecting hair, and obtaining the hair sample after decontamination and drying.

As an optional embodiment, the hair is selected from humans or animals.

As an optional embodiment, the decontamination treatment includes descaling and degreasing the hair with a rinsing liquid.

As an optional embodiment, the rinsing solution is one or more of water, sodium dodecylsulfonate solution, dilute hydrochloric acid solution or methanol solution.

As an optional embodiment, the drying treatment includes drying in an oven, and the drying temperature is controlled at 50-70°C.

As an optional embodiment, the drying treatment includes natural volatilization drying or drying with filter paper.

As an optional implementation, the grinding is performed with a mortar or a special hair grinder.

As an optional embodiment, the magnetic solid-phase extraction microspheres have a porous core-shell structure with a diameter of 0.1-10 μm.

As an optional embodiment, the core layer of the porous core-shell structure is magnetic iron ferric oxide, and the shell layer is porous particles of silica modified with active functional groups.

As an optional embodiment, the added amount of the magnetic solid-phase extraction microspheres is 1/100-1/10 of the hair weight.

As an optional embodiment, the co-solvent comprises a mixture of an organic solvent and a volatile acid or a volatile base.

After the hair is ground, add an appropriate amount of co-solvent to the mixture of hair and magnetic solid-phase extraction microspheres, and continue grinding, so that after the drug to be tested is exposed from the broken hair, under the action of the "bond bridge" of the solution co-agent Adsorbed into the pores on the surface of magnetic SPE microspheres.

The co-solvent can dissolve the drug to be tested, and can provide a solution with a suitable pH environment for the magnetic solid-phase extraction microspheres to adsorb the drug to be tested.

As an optional embodiment, the number of times of adding the co-solvent is several times, and the time for the second grinding is 1-2 minutes.

For the drug to be tested with poor affinity of magnetic solid-phase extraction microspheres, multiple additions of co-solvent and grinding can be adopted until a satisfactory extraction effect is obtained.

As an optional embodiment, the added amount of the co-solvent is enough to wet the hair.

As an optional embodiment, before separating the hair and the magnetic solid-phase extraction microspheres in the second mixture by magnetic attraction, it also includes completely volatilizing the co-solvent.

As an optional embodiment, the separation of hair and magnetic solid-phase extraction microspheres in the second mixture by means of magnetic attraction to obtain magnetic solid-phase extraction microspheres adsorbed with drugs includes:

Transfer the second mixture to a centrifuge tube, make the magnet close to the wall of the centrifuge tube, and shake to separate the magnetic solid-phase extraction microspheres from the hair;

Turn the centrifuge tube upside down and pour out the hair to obtain the magnetic solid-phase extraction microspheres adsorbed with the drug.

Hair debris and magnetic solid phase extraction microspheres are mixed together after grinding, and the magnetic solid phase extraction microspheres are firmly adsorbed on the wall of the centrifuge tube by the magnetic attraction effect of the magnet on the magnetic solid phase extraction microspheres. The hair debris settles to the bottom of the centrifuge tube, realizing the dry separation of the hair debris and the magnetic solid-phase extraction microspheres.

The position of the magnet should be in the middle of the centrifuge tube, so that the magnetic solid-phase extraction microspheres gather in the middle of the centrifuge tube, so that the hair debris can fall down by gravity during the shaking process and be separated from the magnetic solid-phase extraction microspheres.

In the traditional extraction process of drug residues in hair, the hair is first ground into crumbs, then added to the extraction solution for extraction, and then the hair debris is separated, and then the magnetic solid phase extraction microspheres are added to the extraction solution to absorb the to-be-tested substance in the solution. Drugs are separated from the solution and magnetic solid-phase extraction microspheres by magnetic suction, which involves many steps, long time and low extraction efficiency. In contrast, the present invention integrates grinding and extraction into one step, and no extraction solution is required in the whole process, realizing dry extraction with simple operation, short time consumption and high extraction efficiency.

As an optional embodiment, after obtaining the magnetic solid-phase extraction microspheres adsorbed with the drug, it also includes performing purification treatment on the magnetic solid-phase extraction microspheres.

As an optional embodiment, the purification process includes using a solvent to remove impurities, elute, dry and redissolve the magnetic solid phase extraction microspheres to obtain the sample to be tested.

Taking the separation and detection of clenbuterol drug in wool as an example, the present invention will be further described:

1. Acquisition of wool samples

A 7-month-old male small-tailed Han sheep was used as the experimental sheep, and 15 μg/kg body weight of clenbuterol aqueous solution was orally administered once a day, and after 14 days of continuous gavage, the hair on the back of the sheep was cut off, and it was used as a clenbuterol-positive wool sample .

2. Decontamination and drying of wool samples

Put about 2g of clenbuterol-positive wool sample in 100mL of 0.1% sodium dodecylsulfonate solution, ultrasonically wash for 10min, discard the sodium dodecylsulfonate solution, then add 100mL of water and ultrasonically rinse for 5min, and rinse continuously 3 times, take out the hair and put it on the filter paper to dry naturally, then cut it into a length of about 0.5cm with scissors, and set it aside.

3. Hair Grinding

Weigh 0.2 g of the dried hair sample and place it in a mortar, add 0.01 g of magnetic solid-phase extraction microspheres with surface-modified sulfonate ions to it, and grind it with a grinding rod until the hair breaks into crumbs.

4. Drug extraction

Add 0.5 mL of formic acid-methanol (volume ratio 1:500) dropwise to the mixture of hair scraps and magnetic solid-phase extraction microspheres, continue grinding for 1 min, and let stand until the solution evaporates completely.

5. Magnetic solid-phase extraction microsphere separation

Transfer the mixture of hair debris and magnetic SPE microspheres to a 50mL plastic centrifuge tube, then place the centrifuge tube on the magnet test tube rack, and the magnet is located in the middle of the side of the centrifuge tube; then, place the magnet test tube rack on the multi-tube vortex Shake on the vortex shaker for 5 minutes, remove the magnet test tube rack from the multi-tube vortex shaker, turn the magnet test tube rack upside down, beat, and pour out the hair debris.

6. Purification

Remove the centrifuge tube from the magnet test tube rack, add 10mL water-methanol (volume ratio 1:1) mixed solution to it to remove impurities adsorbed on the magnetic SPE microspheres, vortex for 1min, and then place the centrifuge tube in the magnet test tube Put it on the shelf and let it stand still. After the magnetic solid phase extraction microspheres gather around the magnet, suck out the solution with a straw; The clenbuterol was eluted, vortexed for 1min, and then the centrifuge tube was placed on the magnetic test tube rack, and stood still. After the magnetic solid phase extraction microspheres gathered around the magnet, the solution was sucked out with a pipette and transferred to a 10mL centrifuge tube. Medium; dry the solution with nitrogen, add 0.2 mL of water to redissolve the residue, and vortex for 0.5 min to obtain the sample reconstitution solution.

7. Detection

Take the clenbuterol colloidal gold test card and place it horizontally, draw 50 μL of the sample reconstitution solution and drop it into the sample hole of the clenbuterol colloidal gold test card, after standing for 2 minutes, observe the "C" and "T" on the test card A red band was shown everywhere, indicating a positive result for clenbuterol.

It should be noted that in this article, relative terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply these No such actual relationship or order exists between entities or operations. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus comprising a set of elements includes not only those elements, but also includes elements not expressly listed. other elements of or also include elements inherent in such a process, method, article, or device. Without further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article or apparatus comprising said element.

The above descriptions are only specific embodiments of the present invention, so that those skilled in the art can understand or implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Accordingly, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein. .

Claims (10)

1. A method for dry extraction of a drug from hair, comprising:

obtaining a hair sample;

adding magnetic solid phase extraction microspheres into a hair sample for first grinding to obtain a first mixture;

adding a cosolvent into the mixture for second grinding to obtain a second mixture;

separating the hair and the magnetic solid phase extraction microsphere in the second mixture by using a magnetic attraction mode to obtain the magnetic solid phase extraction microsphere adsorbed with the medicine;

wherein the addition amount of the magnetic solid phase extraction microsphere is 1/100-1/10 of the weight of the hair.

2. A method of dry extraction of a drug from hair according to claim 1, wherein obtaining a hair sample comprises: hair was collected, decontaminated and dried to obtain hair samples.

3. The method for extracting the medicine from the hair by the dry method according to claim 1, wherein the magnetic solid phase extraction microsphere has a porous core-shell structure and has a diameter of 0.1-10 μm.

4. A method for dry extraction of a drug from hair according to claim 3, wherein the core layer of the porous core-shell structure is magnetic ferroferric oxide and the shell layer is porous particles of silica modified with active functional groups.

5. A method of dry extraction of a medicament from hair according to claim 1, wherein the co-solvent comprises a mixture of an organic solvent and a volatile acid or base.

6. The method for dry extraction of a drug from hair according to claim 1, wherein the number of addition of the cosolvent is a plurality of times, and the second grinding time is 1 to 2 minutes.

7. The method for dry extraction of a drug from hair according to claim 1, wherein the separating the hair from the magnetic solid phase extraction microsphere in the second mixture by magnetic attraction to obtain the magnetic solid phase extraction microsphere with the drug adsorbed thereon comprises:

transferring the second mixture into a centrifuge tube, enabling the magnet to be clung to the wall of the centrifuge tube, and vibrating to separate the magnetic solid-phase extraction microspheres from the hair;

and (3) reversely buckling the centrifuge tube, and pouring out the hair to obtain the magnetic solid-phase extraction microsphere adsorbed with the medicine.

8. The method for dry extraction of drugs from hair according to claim 1, wherein the magnetic solid phase extraction microsphere with drugs adsorbed thereon is obtained and then further comprises purifying the magnetic solid phase extraction microsphere.

9. The method of claim 1, wherein the step of completely volatilizing the cosolvent is further included before magnetically separating the hair from the magnetic solid phase extraction microspheres in the second mixture.

10. A method of dry extraction of a medicament from hair according to any one of claims 1 to 9 wherein the decontamination treatment comprises descaling and degreasing the hair with a rinse solution employing one or more of clear water, sodium dodecyl sulphate solution, dilute hydrochloric acid solution or methanol solution.

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