CN112213294A - Method for rapidly detecting sildenafil in health-care product - Google Patents
Method for rapidly detecting sildenafil in health-care product Download PDFInfo
- Publication number
- CN112213294A CN112213294A CN202011001696.1A CN202011001696A CN112213294A CN 112213294 A CN112213294 A CN 112213294A CN 202011001696 A CN202011001696 A CN 202011001696A CN 112213294 A CN112213294 A CN 112213294A
- Authority
- CN
- China
- Prior art keywords
- health
- solution
- nano silver
- health product
- silver sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- G01N1/34—Purifying; Cleaning
-
- 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
-
- 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
- G01N1/4055—Concentrating samples by solubility techniques
-
- 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
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
Abstract
A method for rapidly detecting sildenafil in a health-care product comprises the following steps: s1: pretreating a sample, taking a proper amount of health product pills, grinding into solid powder, putting into a centrifuge tube, adding 1-3mL of ethyl acetate solution, and performing ultrasonic extraction for 2-5min to obtain a health product solution; s2: centrifuging the obtained health product solution to be clear, taking 1 volume of supernatant, adding 0.5 volume of acid solution into the taken supernatant for back extraction, shaking and mixing, standing for layering, and taking a water phase layer to be detected; s3: and (3) adding the nano silver sol, the sample to be detected and the agglomerating agent into a Raman detection bottle, and uniformly mixing to perform Raman spectrum detection. The method overcomes the defects of the prior art, and utilizes the plasmon resonance effect of the metal silver nanoparticles under laser irradiation, so that the Raman signal of the illegal additives with low content in the health care product is enhanced, and the rapid and accurate detection of the illegal additives in the health care product is realized.
Description
Technical Field
The invention relates to the technical field of drug detection, in particular to a method for rapidly detecting sildenafil in a health-care product.
Background
Sildenafil, a drug for the treatment of male erectile dysfunction, was first used for the treatment of cardiovascular diseases, mainly by selectively inhibiting phosphodiester (PDE5), thereby increasing cyclic guanosine monophosphate (cGMP) levels, causing relaxation of the cavernous smooth muscle, blood influx, and engorgement of the penis, erection. Sildenafil has a lot of side effects when being used as a medicine, and at present, the widely known medicines mainly comprise headache, dyspepsia, visual disturbance, flushing and even sudden death in severe cases, and belong to medicines strictly regulated by the state.
At present, some illegal manufacturers illegally add sildenafil into health care products to achieve the effects of resisting fatigue and increasing resistance, which is very dangerous for consumers. Therefore, it is necessary to develop a method for accurately detecting the illegally added sildenafil and other medicines in the health care product. The conventional detection method mainly comprises high performance liquid chromatography tandem mass spectrometry which has an excellent detection limit, but the detection process is complex, long in time consumption and high in detection cost, and is difficult to popularize and apply universally.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for rapidly detecting sildenafil in a health-care product, overcomes the defects of the prior art, meets the detection requirement of sildenafil in the health-care product, and has the characteristics of convenience, rapidness, high sensitivity and low cost.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for rapidly detecting sildenafil in a health-care product comprises the following steps:
step S1: pretreating a sample, taking a proper amount of health product pills, grinding into solid powder, putting into a centrifuge tube, adding 1-3mL of ethyl acetate solution, and performing ultrasonic extraction for 2-5min to obtain a health product solution;
step S2: centrifuging the obtained health product solution to be clear, taking 1 volume of supernatant, adding 0.5 volume of acid solution into the taken supernatant for back extraction, shaking and mixing, standing for layering, and taking a water phase layer to be detected;
step S3: and (3) adding the nano silver sol, the sample to be detected and the agglomerating agent into a Raman detection bottle, and uniformly mixing to perform Raman spectrum detection.
Preferably, the acid solution in step S2 includes hydrochloric acid, sulfuric acid, acetic acid, nitric acid and their mixture in any ratio.
Preferably, the nano silver sol in the step S3 has a particle size of 40 to 60 nm.
Preferably, the preparation method of the nano silver sol in step S3 includes the following steps:
step S31: weighing 30mg of silver nitrate, and dissolving the silver nitrate in 150mL of deionized water;
step S32: after boiling, adding 2-3mL of 1% sodium citrate dihydrate, stirring at high speed for 1-2h, and cooling to room temperature;
step S32: and screening to obtain the nano silver sol.
Preferably, the agglomerating agent in the step S3 is one of an inorganic salt solution, a sodium salt solution, a magnesium salt solution, a calcium salt solution, a potassium salt solution or a mixed salt solution.
Preferably, the nano silver sol in the step S3 is an untreated nano silver sol or a concentrated nano silver sol.
Preferably, the adding ratio of the nano silver sol, the sample to be detected and the agglomerating agent in the step S3 is 5: 1-5: 0-2.
The invention provides a method for rapidly detecting sildenafil in a health-care product. The method has the following beneficial effects: according to the invention, through the steps of extraction, centrifugation and back extraction, the pretreatment process can be completed within 5-6min, and finally the detection of a sample to be detected is completed within 1min by using a surface plasmon Raman spectroscopy technology, so that a Raman spectrum with molecular fingerprint information is obtained; the surface plasmon enhanced Raman spectrum spectrogram obtained by the sample to be detected can be compared with the standard surface plasmon enhancement of the sample, so that whether the sample to be detected contains molecules to be detected or not is judged, the whole data analysis process is an automatic process, and no human intervention is caused.
Drawings
In order to more clearly illustrate the present invention or the prior art solutions, the drawings that are needed in the description of the prior art will be briefly described below.
FIG. 1 is a plot of Raman spectral signatures of a sildenafil pure sample standard;
FIG. 2 is a surface enhanced Raman spectrum of four health products detected by the nano-silver sol;
FIG. 3 is a surface enhanced Raman spectrum of four health products detected by the concentrated nano silver sol in the example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings.
The invention discloses a method for rapidly detecting sildenafil in a health-care product, which comprises the following steps:
step S1: pretreating a sample, taking a proper amount of health product pills, grinding into solid powder, putting into a centrifuge tube, adding 2mL of ethyl acetate solution, and performing ultrasonic extraction for 4min to obtain a health product solution;
in the step, the ethyl acetate is added to realize extraction of sildenafil in the health-care product, the pills of the health-care product are crushed into solid powder to enable the health-care product to be in contact with the ethyl acetate serving as an organic solvent in the largest area, so that the extraction efficiency is improved, 2mL of ethyl acetate is added, the particles of the health-care product can be submerged mainly according to the volume ratio, and the added amount cannot enable the concentration of the extracted sildenafil to be too low to influence the sensitivity of subsequent detection.
Step S2: centrifuging the obtained health product solution to be clear, taking 1mL of supernatant, adding 0.5mL of acid solution into the taken supernatant for back extraction, shaking and mixing, standing for layering, and taking a water phase layer to be detected;
the acid solution in the step comprises hydrochloric acid, sulfuric acid, acetic acid, nitric acid and mixed solution thereof in any proportion.
In the step, 1mL of the health care product solution obtained by ultrasonic extraction is taken and centrifuged to obtain a clear solution, so that impurities in the solution are removed. And back-extracting the clarified liquid obtained by centrifugation, and adding an acid solution into the test tube, wherein the effect of the acid solution is mainly that the dissolution amount of sildenafil in the acid solution is superior to that of an organic solvent, so that an aqueous solution of sildenafil is obtained. The volume ratio of the acid liquid to the clarified liquid is 1: 2, wherein the concentration of the acid solution is preferably 45mg/kg, too high concentration can lead to aggregation of the nanoparticles of the subsequent metal, thereby rendering the detection ineffective, and too low concentration can lead to poor back extraction effect, thereby reducing the detection sensitivity.
Step S3: and (3) adding the nano silver sol, the sample to be detected and the agglomerating agent into a Raman detection bottle, and uniformly mixing to perform Raman spectrum detection.
Specifically, the nano silver sol used in step S3 has a particle size of 40 to 60 nm.
Wherein the screening synthesis of the nano silver sol comprises the following steps:
step S31: weighing 30mg of silver nitrate, and dissolving the silver nitrate in 150mL of deionized water;
step S32: after boiling, adding 2-3mL of 1% sodium citrate dihydrate, stirring at high speed for 1-2h, and cooling to room temperature;
step S32: and screening to obtain the nano silver sol.
In several experiments according to the above method, 30mg of silver nitrate was weighed and dissolved in 150mL of deionized water, 2mL and 3mL of 1% sodium citrate dihydrate were added after boiling, stirred at high speed for 1 hour and 1.5 hours, cooled to room temperature, and screened to find that the Raman enhancement effect of the nanosol obtained under the reaction conditions of 2mL of 1% sodium citrate dihydrate and high speed stirring for 1 hour was the best.
Further, in step S3, the agglomerating agent is one of an inorganic salt solution, a sodium salt solution, a magnesium salt solution, a calcium salt solution, a potassium salt solution or a mixed salt solution.
Further, there are two kinds of silver sols used for raman detection, one is untreated silver sol obtained by reaction, and the other is concentrated silver sol. The concentrated silver sol is mainly prepared by adding untreated silver sol into a centrifugal tube, centrifuging, separating the centrifugal tube into supernate and silver nanoparticle sediment at the bottom, taking out the supernate, continuing adding the silver sol, oscillating, dispersing the sediment at the bottom into the newly added silver sol, and then centrifuging again, repeating the steps for 2-3 times to obtain the concentrated silver sol. In the silver sol with the same volume, the quantity of the nano particles in the concentrated silver sol is more than that of the untreated silver sol, namely the nano particles have smaller intervals and better reinforcing effect, and the detection can be carried out on the solution to be detected with lower concentration.
Further, in the step S3, the adding ratio of the nano silver sol, the sample to be detected, and the agglomerating agent is 5: 1-5: 0-2. The agglomeration agent mainly reduces the spacing between the silver nano particles, enhances the detection effect of Raman, does not need to be added when the content of contraband in the health care product is higher, namely the detection effect of the nano silver sol is better, and can reduce the detection limit by adding the agglomeration agent and increasing the addition of the agglomeration agent when the detection effect is not good.
Example one
The method for detecting sildenafil in different health-care products comprises the following specific steps:
sample pretreatment: grinding about half of different health product pills, adding into 5mL centrifuge tube, adding 2mL ethyl acetate, and ultrasonic extracting for 4 min; centrifuging the solution after ultrasonic extraction for 2min, collecting 1mL of supernatant, adding 0.5mL of hydrochloric acid solution, oscillating for 30s, standing for layering into water phase and organic phase, and collecting the lower layer as the solution to be detected and the water phase.
And (3) detection: respectively taking 1mL of untreated and concentrated nano-silver sol into a Raman detection bottle, taking 200uL of to-be-detected liquid, placing the to-be-detected liquid into the detection bottle, then adding 200uL of an aggregating agent NaCl solution, uniformly mixing, and detecting on a handheld Raman spectrometer, wherein the detection results of the untreated silver sol and the concentrated silver sol are shown in attached figures 2-3.
The invention uses organic solvent ethyl acetate to extract sildenafil in the health care product, centrifugalizes to remove impurities, and then uses acid liquor to carry out back extraction to obtain sildenafil aqueous solution; the method combines the surface enhanced Raman spectroscopy technology, utilizes the silver nanoparticles to enhance the sildenafil signal, eliminates the interference of the substrate, obtains the Raman spectrum signal of the sildenafil, can realize the rapid detection of the sildenafil in different health care products within 8min, has low detection cost, is convenient to operate, and can meet the requirement of actual detection. Fig. 1 is a graph of characteristic signals of raman spectrum of sildenafil, with raman shift on the abscissa and raman signal intensity on the ordinate, and the characteristic peak positions of 650, 814, 1234, 1527, 1579, and the like. Fig. 2 and 3 are surface enhanced raman spectrograms obtained by detecting sildenafil in different health care products by two different silver sols in the embodiment of the invention.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for rapidly detecting sildenafil in a health-care product is characterized by comprising the following steps:
step S1: pretreating a sample, taking a proper amount of health product pills, grinding into solid powder, putting into a centrifuge tube, adding 1-3mL of ethyl acetate solution, and performing ultrasonic extraction for 2-5min to obtain a health product solution;
step S2: centrifuging the obtained health product solution to be clear, taking 1 volume of supernatant, adding 0.5 volume of acid solution into the taken supernatant for back extraction, shaking and mixing, standing for layering, and taking a water phase layer to be detected;
step S3: and (3) adding the nano silver sol, the sample to be detected and the agglomerating agent into a Raman detection bottle, and uniformly mixing to perform Raman spectrum detection.
2. The method for rapidly detecting sildenafil in a health product according to claim 1, wherein the method comprises the following steps: the acid solution in the step S2 includes hydrochloric acid, sulfuric acid, acetic acid, nitric acid and mixed solutions thereof in any proportion.
3. The method for rapidly detecting sildenafil in a health product according to claim 1, wherein the method comprises the following steps: the particle size of the nano silver sol in the step S3 is 40-60 nm.
4. The method for rapidly detecting sildenafil in a health product according to claim 1, wherein the method comprises the following steps: the preparation method of the nano silver sol in the step S3 includes the following steps:
step S31: weighing 30mg of silver nitrate, and dissolving the silver nitrate in 150mL of deionized water;
step S32: after boiling, adding 2-3mL of 1% sodium citrate dihydrate, stirring at high speed for 1-2h, and cooling to room temperature;
step S32: and screening to obtain the nano silver sol.
5. The method for rapidly detecting sildenafil in a health product according to claim 1, wherein the method comprises the following steps: in the step S3, the agglomerating agent is one of inorganic salt solution, sodium salt, magnesium salt, calcium salt, potassium salt solution or mixed salt solution.
6. The method for rapidly detecting sildenafil in a health product according to claim 1, wherein the method comprises the following steps: the nano silver sol in the step S3 is untreated nano silver sol or concentrated nano silver sol.
7. The method for rapidly detecting sildenafil in a health product according to claim 1, wherein the method comprises the following steps: the adding proportion of the nano silver sol, the sample to be detected and the agglomerating agent in the step S3 is 5: 1-5: 0-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011001696.1A CN112213294A (en) | 2020-09-22 | 2020-09-22 | Method for rapidly detecting sildenafil in health-care product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011001696.1A CN112213294A (en) | 2020-09-22 | 2020-09-22 | Method for rapidly detecting sildenafil in health-care product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112213294A true CN112213294A (en) | 2021-01-12 |
Family
ID=74050497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011001696.1A Pending CN112213294A (en) | 2020-09-22 | 2020-09-22 | Method for rapidly detecting sildenafil in health-care product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112213294A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113324978A (en) * | 2021-06-01 | 2021-08-31 | 天津市食品安全检测技术研究院 | Method for detecting calcium and iron in health food |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012041262A1 (en) * | 2010-09-29 | 2012-04-05 | Univerzita Palackeho V Olomouci | Method for activation of aqueous silver nanoparticle dispersions for surface enhanced raman spectroscopy |
| WO2016177002A1 (en) * | 2015-05-04 | 2016-11-10 | 清华大学 | Raman spectroscopy-based method for detecting addition of western medicines into healthcare product |
| CN108613969A (en) * | 2018-08-23 | 2018-10-02 | 普拉瑞思科学仪器（苏州）有限公司 | The rapid detection method of honey element in a kind of white wine |
| CN110333214A (en) * | 2018-11-14 | 2019-10-15 | 厦门市普识纳米科技有限公司 | The detection method of illegal addition drug ingredient in a kind of health care product |
| CN110954525A (en) * | 2019-09-23 | 2020-04-03 | 上海如海光电科技有限公司 | Raman rapid detection method for sibutramine in weight-reducing tea |
| CN111380855A (en) * | 2018-12-29 | 2020-07-07 | 同方威视技术股份有限公司 | Method for screening illegal drugs in health care products on site |
-
2020
- 2020-09-22 CN CN202011001696.1A patent/CN112213294A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012041262A1 (en) * | 2010-09-29 | 2012-04-05 | Univerzita Palackeho V Olomouci | Method for activation of aqueous silver nanoparticle dispersions for surface enhanced raman spectroscopy |
| WO2016177002A1 (en) * | 2015-05-04 | 2016-11-10 | 清华大学 | Raman spectroscopy-based method for detecting addition of western medicines into healthcare product |
| CN108613969A (en) * | 2018-08-23 | 2018-10-02 | 普拉瑞思科学仪器（苏州）有限公司 | The rapid detection method of honey element in a kind of white wine |
| CN110333214A (en) * | 2018-11-14 | 2019-10-15 | 厦门市普识纳米科技有限公司 | The detection method of illegal addition drug ingredient in a kind of health care product |
| CN111380855A (en) * | 2018-12-29 | 2020-07-07 | 同方威视技术股份有限公司 | Method for screening illegal drugs in health care products on site |
| CN110954525A (en) * | 2019-09-23 | 2020-04-03 | 上海如海光电科技有限公司 | Raman rapid detection method for sibutramine in weight-reducing tea |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113324978A (en) * | 2021-06-01 | 2021-08-31 | 天津市食品安全检测技术研究院 | Method for detecting calcium and iron in health food |
| CN113324978B (en) * | 2021-06-01 | 2023-08-01 | 天津市食品安全检测技术研究院 | Method for detecting calcium and iron in health food |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103398998B (en) | A kind of Raman microprobe for mercury ion detecting and preparation method thereof | |
| Collasiol et al. | Ultrasound assisted mercury extraction from soil and sediment | |
| CN104101591A (en) | Fast detection method for surface enhanced Raman scattering of trace pesticide residues in oranges | |
| Liu et al. | Liquid–liquid interfacial self-assembled Au NP arrays for the rapid and sensitive detection of butyl benzyl phthalate (BBP) by surface-enhanced Raman spectroscopy | |
| Li et al. | Fabrication of pollutant-resistance SERS imprinted sensors based on SiO2@ TiO2@ Ag composites for selective detection of pyrethroids in water | |
| Bi et al. | A fluorescence turn-off-on chemosensor based on carbon nanocages for detection of ascorbic acid | |
| CN107037029A (en) | It is a kind of based on detection method of the gold nanorods SERS substrates to drugs in human body fluid | |
| Zhao et al. | Sensitive surface-enhanced Raman scattering for the quantitative detection of formaldehyde in foods using gold nanorod substrate | |
| CN111380855A (en) | Method for screening illegal drugs in health care products on site | |
| CN112213294A (en) | Method for rapidly detecting sildenafil in health-care product | |
| Zolfonoun et al. | Preconcentration procedure using vortex-assisted liquid–liquid microextraction for the fast determination of trace levels of thorium in water samples | |
| Yang et al. | SERS detection of benzoic acid in milk by using Ag-COF SERS substrate | |
| Atta et al. | Ultra-high SERS detection of consumable coloring agents using plasmonic gold nanostars with high aspect-ratio spikes | |
| CN111024665A (en) | Method for measuring content of organic selenium in selenium-enriched rice or product prepared from selenium-enriched rice | |
| Mortada et al. | Preconcentration of aluminum by dual-cloud point extraction and its determination by inductively coupled plasma-optical emission spectrometry | |
| CN114778515A (en) | Method for simultaneously detecting sibutramine and fenfluramine in weight-losing health-care product | |
| Guo et al. | Raman enhancement effect of different silver nanoparticles on salbutamol | |
| CN107748153B (en) | Penicillium amine probe with fluorescence-ultraviolet dual-signal mode and application thereof | |
| CN104330396A (en) | Method for rapidly detecting rhodamine B in food | |
| CN103776772B (en) | A kind of method of the circular dichroism signal detection DNA assembled based on gold nano cone | |
| WO2024001287A1 (en) | Preparation method for and use of mofs-based composite pretreated material for eliminating cap interference | |
| CN110954525A (en) | Raman rapid detection method for sibutramine in weight-reducing tea | |
| CN106634983A (en) | Nitrogen-sulfur-doped fluorescent carbon quantum dot and preparation method and application thereof | |
| CN114965418A (en) | Method for rapidly detecting mercury by surface enhanced Raman scattering | |
| CN113237857A (en) | Application of perovskite quantum dots in detection of content of heavy metal ions in edible oil and detection method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |