CN109212105B - Liquid chromatography-mass spectrometry detection method for textile salicylate ultraviolet-proof finishing agent - Google Patents
Liquid chromatography-mass spectrometry detection method for textile salicylate ultraviolet-proof finishing agent Download PDFInfo
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Abstract
The invention discloses a liquid chromatography-mass spectrometry detection method of textile salicylate ultraviolet-proof finishing agent, which comprises the following steps: preparing a sample to be detected into a sample solution to be detected; preparing 7 salicylic acid ester ultraviolet-proof finishing agents into a gradient standard working solution; injecting the gradient standard working solution into a liquid chromatogram-tandem mass spectrometer, measuring in a positive and negative ion multi-reaction monitoring mode, and making a standard curve equation; and detecting the sample solution to be detected according to the method, thereby obtaining the content of the 7 salicylic acid ester ultraviolet-proof finishing agents in the sample to be detected. The liquid chromatography-tandem mass spectrometry method is qualitative and quantitative, has high sensitivity, and is suitable for detecting the salicylate ultraviolet-proof finishing agent in the textile.
Description
Technical Field
The invention relates to a liquid chromatography-tandem mass spectrometry detection method suitable for a salicylate ultraviolet-proof finishing agent in textiles.
Background
Ultraviolet rays can cause skin tanning, sunburn and even induce skin cancer. With the gradual and deep understanding of ultraviolet radiation in sunlight and the harm to human health, people strive to explore various methods capable of reducing the damage of ultraviolet to human health, wherein ultraviolet-proof clothes become indispensable equipment for outdoor sports. The garment materials made of natural fibers or conventional chemical fibers generally cannot meet the requirements of ultraviolet radiation resistance. Functional textiles can generally be obtained by applying functional fibers and functional after finishing. The protection principle is as follows: the fiber, yarn or fabric is treated with a chemical agent that absorbs and shields the fibers, yarn or fabric. Salicylate-based uv absorbers are the first to be used, and salicylates have intrinsic hydrogen bonds in the molecule. The ultraviolet absorbent has very low ultraviolet absorption capacity at the beginning and extremely narrow absorption range (less than 340nm), but after ultraviolet irradiation for a certain time, the absorption of the ultraviolet absorbent is gradually increased until the maximum absorption, because the ultraviolet absorbent can generate 2-hydroxybenzophenone with strong ultraviolet absorption capacity through the Photo-Fries rearrangement under the action of light, and the compounds can be used as the ultraviolet absorbent to strengthen the ultraviolet absorption effect, and the rearrangement reaction can be represented by the following formula:
therefore, it is called precursor type ultraviolet absorber, and its main species are: phenyl salicylate, p-tert-butylphenyl salicylate, p-tert-octylphenyl salicylate, resorcinol monobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, 2-ethylhexyl salicylate, and trimethylcyclohexyl salicylate. The 7 salicylate ultraviolet-proof finishing agents are precursor compounds of benzophenone compounds, and can generate the benzophenone compounds with strong ultraviolet absorption capacity by Photo-Fries rearrangement under the action of light.
However, benzophenone compounds have irritation and anesthetic effects, and can cause headache, nausea, vomiting, dizziness, somnolence, dysesthesia, emotional dysphoria and other reactions after long-term contact. Especially recent studies have shown that: benzophenone compounds are environmental endocrine disruptors, which cause endocrine dysfunction in various organisms including humans, poultry and wild animals, decrease in the function of the human reproductive system and male estrification of animals, and are also associated with the discharge of endocrine disruptors such as benzophenones. Thus, the influence of salicylate-based ultraviolet absorbers on humans and the ecological environment is not insignificant. At present, no research report on a detection method of a salicylate ultraviolet-proof finishing agent in related textiles exists at home, and only a report on a detection method of a part of ultraviolet absorbers in cosmetics and food packaging materials exists. The ecological production, the ecological consumption and the ecological treatment of textile products are inevitable trends, the development of ecological textiles is related to the export and earning level of textile products in China, is related to the strategy of sustainable development of the industry, and plays a very important role in strengthening the doing-the-job textile industry in China. In order to maintain the basic safety of the country, guarantee the health of human beings, protect the ecological environment, break through the technical trade barrier of developed countries, also in order to push out clean production and promote the technical development level of enterprises, the method for detecting the salicylate ultraviolet-proof finishing agent in the fabric has important practical significance.
In the high performance liquid chromatography for measuring the content of salicylate ultraviolet absorbers in the sunscreen cosmetics, the content of 8 salicylate ultraviolet absorbers (ethylhexyl salicylate, trimethylcyclohexyl salicylate, octyl salicylate, phenyl salicylate, isocetyl salicylate, hexyl salicylate, glycol salicylate and benzyl salicylate) in the sunscreen cosmetics is simultaneously measured by the high performance liquid chromatography. The sample is extracted by 5mL ethyl acetate at 20 ℃ for 10min by ultrasound, and the extract is extracted by Agilent ZORBAX Eclipse XDB-C18Separating on chromatographic column, and gradient eluting with methanol-tetrahydrofuran-0.1% (by mass) formic acid solution as mobile phase, with ultraviolet detection wavelength of 340 nm. In the peak formation, the simultaneous determination of oxybenzone 5 sulfonic acid, sodium salicylate, oxybenzone and phenyl salicylate by the high performance liquid chromatography researches on the mu-Bondapak C by taking methanol tetrahydrofuran water as a mobile phase18Separating and measuring chromatographic conditions of ultraviolet absorbers such as oxybenzone 5 sulfonic acid, sodium salicylate, oxybenzone, phenyl salicylate, etc. on the column, with ultraviolet detection wavelength of 310 nm. These studies are limited to HPLC analysis methods for determining a part of UV absorbers in sunscreen cosmetics, and the detection wavelength is also limited to a single wavelength, and the characteristic UV absorption wavelengths of various salicylate UV absorbers cannot be more fully characterized, so that the false positive samples cannot be confirmed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a liquid chromatogram-tandem mass spectrometry method which is qualitative, quantitative and high in sensitivity and is suitable for detecting the salicylate ultraviolet-proof finishing agent in the textile.
In order to solve the technical problems, the invention provides a liquid chromatography-tandem mass spectrometry detection method (suitable for detecting salicylate ultraviolet-proof finishing agents in textiles) for a textile salicylate ultraviolet-proof finishing agent, which is characterized by comprising the following steps:
1) preparing a sample solution to be detected:
shearing a sample to be detected, adding an extracting agent for ultrasonic extraction, cooling the obtained extracting solution to room temperature, and filtering by using a 0.20-0.45 mu m filter head to obtain a sample solution to be detected;
the purpose is to carry out qualitative and quantitative analysis on UPLC-MS/MS; namely, a liquid chromatogram-mass spectrometer is adopted for measurement, and the quantification is carried out by an external standard method;
2) preparing a standard solution:
dissolving 7 salicylic acid ester ultraviolet-proof finishing agents with the same concentration by using an organic solvent to form a mixed standard working solution (namely, the concentrations of the 7 salicylic acid ester ultraviolet-proof finishing agents in the mixed standard working solution are consistent);
performing gradient dilution (with an organic solvent) on the mixed standard working solution to form a gradient standard working solution;
generally, preparing a mixed standard working solution of 0.1-10 mu g/mL;
3) injecting the gradient standard working solution into a liquid chromatogram-tandem mass spectrometer, measuring in a positive and negative ion Multiple Reaction Monitoring (MRM) mode, determining the peak-out positions of 7 salicylic acid ester ultraviolet-proof finishing agents, recording the peak areas (recording the corresponding peak areas) of quantitative ion pairs, and making a standard curve equation by taking the concentration as a horizontal coordinate and the peak areas as a vertical coordinate;
remarks explanation: the concentration refers to the concentration of 7 salicylic acid ester ultraviolet-proof finishing agents in the gradient standard working solution, namely the concentration set in the step 2);
4) and taking the sample solution to be detected (supernatant) obtained in the step 1) to determine peak areas of 7 salicylic acid ester ultraviolet-proof finishing agents in the sample solution to be detected according to the method in the step 3), and calculating according to the standard curve equation obtained in the step 3) to obtain the content of the 7 salicylic acid ester ultraviolet-proof finishing agents in the sample to be detected.
As an improvement of the LC-MS detection method of the textile salicylate ultraviolet-proof finishing agent of the present invention, the 7 salicylate ultraviolet-proof finishing agents: phenyl salicylate, p-tert-butylphenyl salicylate, p-tert-octylphenyl salicylate, resorcinol monobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, 2-ethylhexyl salicylate and trimethylcyclohexyl salicylate. Specifically as described in table 1.
The invention is further improved by a liquid chromatography-mass spectrometry detection method of the textile salicylate ultraviolet-proof finishing agent:
firstly, the liquid chromatography conditions (liquid chromatography conditions for ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) of step 3) are as follows:
the mobile phase consists of acetonitrile and water; the gradient elution procedure was: the water accounts for 80-20% of the volume of the mobile phase from the beginning to 2min, the water accounts for 20% of the volume of the mobile phase when the volume is more than 2min to 4min, and the water accounts for 20-80% of the volume of the mobile phase when the volume is more than 4min to 6 min; flow rate: 0.2-0.8 mL/min; column temperature: 20-45 ℃; sample introduction volume: 1-10 mu L;
namely, mobile phase a: water; mobile phase B: acetonitrile; gradient elution procedure: 0-2 min, 80-20% of A; 2-4 min, 20% A-20% A; 4-6 min, 20-80% of A.
Secondly, the mass spectrum conditions for the liquid chromatogram-tandem mass spectrum detection in the step 3) are as follows:
the ion source is an electrospray ion source (ESI); the detection mode is a positive and negative ion Multiple Reaction Monitoring (MRM) mode; the capillary voltage is 2-4 kV; the temperature of the ion source is 80-150 ℃; the temperature of the desolventizing gas is 150-380 ℃; the desolventizing air flow rate is 200-800L/h; the flow speed of the cone hole back blowing air is 10-60L/h; the residence time of the ions is 0.03-0.2 s; the voltage of the taper hole is 10-40V; the collision voltage is 5-30V;
the quantitative ion pair of phenyl salicylate is 213.1 to 169.09, the qualitative ion pair is 213.1 to 107.15, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of resorcinol monobenzoate is 213.24-169.2, the qualitative ion pair is 213.24-121.04, and the monitoring mode of negative ion multiple reaction is adopted;
the quantitative ion pair of the salicylic acid-p-tert-butyl phenyl ester is 269.6-149.155, the qualitative ion pair is 269.6-225.35, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the p-dimethylaminobenzoic acid-2-ethylhexyl ester is 278.55>151.13, the qualitative ion pair is 278.55>166.21, and the positive ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the salicylic acid-2-ethylhexyl ester is 249.47>136.99, the qualitative ion pair is 249.47>92.98, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the trimethyl cyclohexyl salicylate is 261.3 to 136.99, the qualitative ion pair is 261.3 to 92.99, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the salicylic acid-p-tert-octylphenyl ester is 325.29-205.44, the qualitative ion pair is 325.29-281.31, and the mode of negative ion multiple reaction monitoring is adopted.
That is, the parameters of quantitative ion pair, qualitative ion pair, ion residence time, cone hole voltage, collision voltage, etc. are shown in table 2.
As a further improvement of the LC-MS detection method of the textile salicylate ultraviolet-proof finishing agent, the LC column comprises: acquity
BEH C18100mm × 2.1mm, 1.7 μm chromatography column or equivalent.
The invention is further improved by a liquid chromatography-mass spectrometry detection method of the textile salicylate ultraviolet-proof finishing agent: the organic solvent in the step 2) is methanol or acetonitrile; the extracting agent in the step 1) is methanol or acetonitrile;
and the organic solvent in step 2) is the same as the extractant in step 1) (i.e., the organic solvent, the extractant must be methanol at the same time, or acetonitrile at the same time).
The invention is further improved by a liquid chromatography-mass spectrometry detection method of the textile salicylate ultraviolet-proof finishing agent: the step 1) is as follows:
1.1) cutting a sample to be detected into small pieces of 5mm multiplied by 5mm to be used as a sample;
1.2) putting the sample and the extractant into an extractor together according to the material-liquid ratio of 1 g/10-50 mL, sealing the extractor, and performing ultrasonic extraction at room temperature for 10-60 min.
The invention is further improved by a liquid chromatography-mass spectrometry detection method of the textile salicylate ultraviolet-proof finishing agent: the step 1) is as follows:
gradient standard working solutions with the concentrations of the salicylate ultraviolet-proof finishing agent respectively being 0.1 mu g/mL, 0.3 mu g/mL, 0.5 mu g/mL, 0.7 mu g/mL and 1.0 mu g/mL are set.
TABLE 1.7 chemical information table of ultraviolet-proof finishing agents of salicylates
TABLE 2.7 Mass Spectrometry Condition Table of salicylic acid ester type anti-ultraviolet finishing agent
Note: ion pairs were used for quantification.
The liquid chromatography-tandem mass spectrometry adopted by the invention not only can obtain the detection lower limit with the best sensitivity, but also can accurately, qualitatively and quantitatively determine the target compound. The invention optimizes the response values of ions with different charges in an electrospray ionization source (ESI), adopts a detection mode of simultaneously monitoring positive ions and negative ions of the electrospray ionization source (ESI), realizes one-time detection of various salicylate ultraviolet-proof finishing agents with different ions, utilizes the unique ultrahigh pressure liquid chromatography advantage of an Ultrahigh Performance Liquid Chromatography (UPLC) system and all the potential and advantages of small particles of a BEH microcrystalline column, continuously and greatly improves the detection speed and simultaneously greatly improves the detection sensitivity. The method has the advantages of high sensitivity, simple and convenient operation, accuracy, reliability, and obvious advancement and innovation.
Compared with the prior art, the invention has the following remarkable technical effects:
(1) by adopting an electrospray ionization (ESI) detection mode of simultaneously monitoring positive ions and negative ions, the UPLC-MS/MS method has the characteristics of accuracy, qualitative and quantitative performance and high flexibility length, can be used for directly carrying out detection at one time, and the obtained result can be used for confirming the liquid chromatography detection result and is more accurate and reliable.
(2) The method utilizes the special ultrahigh pressure advantage of an Ultra Performance Liquid Chromatography (UPLC) system and all the potential and advantages of small particles of a BEH microcrystalline column, has extremely low bonded phase loss and extremely low UPLC-MS/MS background signal, is particularly beneficial to obtaining higher analysis speed of the compound while improving the separation degree, and obtains higher sensitivity because the chromatographic peak becomes narrower and the peak height is higher. The electrospray positive and negative ion modes are adopted for simultaneous monitoring, the total ion current chromatogram of different salicylate ultraviolet-proof finishing agents is simultaneously acquired in time intervals by 4 channels, and the sensitivity of the detection method is greatly improved.
(3) The determination method disclosed by the invention has a good linear relation of 0.01-1.0 mu g/mL, the linear correlation coefficient is more than 0.99, the lowest limit of detection (LOD) of the method is 0.06 mu g/kg, and the lowest limit of quantitative detection (LOQ) of the method is 0.19 mu g/kg.
The sample extraction method provided by the invention adopts an ultrasonic extraction method, and is simple to operate and high in extraction efficiency. The ultra-high performance liquid chromatography-tandem mass spectrometry can quickly and accurately separate and measure 7 salicylate ultraviolet-proof finishing agents within 4 minutes, and the method has the advantages of high sensitivity, simple and convenient operation, accuracy, reliability, and obvious advancement and innovation.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an ultra-high performance liquid chromatography-tandem mass spectrometry total ion current chromatogram of 7 salicylic acid ester ultraviolet-proof finishing agents.
In FIG. 1, the total ion chromatogram of 2-ethylhexyl salicylate (2-ethylhexyl salicylate), tricyclohexyl salicylate (homosalate), p-Tert-octylphenyl salicylate (4-octylphenyl salicylate), p-Tert-butylphenyl salicylate (4-Tert-butylphenyl salicylate), 2-ethylhexyl p-dimethylaminobenzoate (2-ethylhexyl 4-dimthyllaminobenzoate), phenyl salicylate (2-epoxyphenylbenzoate), and resorcinol monobenzoate (Benzoic acid 3-hydroxyphenyl) are shown in this order.
FIGS. 2 to 5 are mass spectrograms of the ultra-high performance liquid chromatography-tandem mass spectrometry multiple reaction ion monitoring of 7 salicylic acid ester anti-ultraviolet finishing agents.
Wherein:
FIG. 2: an ultra-high performance liquid chromatography-tandem mass spectrometry multiple reaction monitoring mass spectrogram of 2-ethylhexyl salicylate (2-ethylhexyl salicylate), tricyclohexyl salicylate (homosalate) and 4-tert-octylphenyl salicylate (4-octylphenyl salicylate) in the channel 2 is arranged from top to bottom;
FIG. 3: an ultra performance liquid chromatography-tandem mass spectrometry multi-reaction monitoring mass spectrogram of salicylic acid-p-Tert-butyl phenyl salicylate (4-Tert-butyl phenyl salicylate) in the channel 4 is arranged from top to bottom;
FIG. 4: an ultra-performance liquid chromatography-tandem mass spectrometry multi-reaction monitoring mass spectrogram of 2-ethylhexyl p-dimethylaminobenzoate (2-ethylhexyl 4-dimethylamino benzoate) in the channel 3 is arranged from top to bottom;
FIG. 5: the mass spectrograms of the ultrahigh performance liquid chromatography-tandem mass spectrometry multiple reaction monitoring of phenyl salicylate (2-phenoxyphenyl) and resorcinol monobenzoate (Benzoic acid 3-hydroxyphenyl) in the channel 1 are sequentially arranged from top to bottom.
Detailed Description
The present invention is illustrated below by referring to examples and comparative examples, however, the scope of the present invention is not limited to only the following examples. Those of ordinary skill in the art, with the benefit of the present disclosure, will be able to implement the present invention as a result of the present disclosure. 1 reagents and materials
Unless otherwise indicated, all reagents used in the analysis were HPLC grade and all water was first grade water.
1.1 methanol.
1.2 acetonitrile.
1.3 salicylic acid ester ultraviolet-proof finishing agent standard substance: phenyl salicylate (purity is more than or equal to 98%), salicylic acid-p-tert-butyl phenyl ester (purity is more than or equal to 98%), salicylic acid-p-tert-octyl phenyl ester (purity is more than or equal to 98%), resorcinol monobenzoate (purity is more than or equal to 98%), p-dimethylaminobenzoic acid-2-ethylhexyl ester (purity is more than or equal to 98%), salicylic acid-2-ethylhexyl ester (purity is more than or equal to 98%), trimethylcyclohexyl salicylate (purity is more than or equal to 98%), and the like.
1.4 Standard stock solutions: preparing 7 salicylic acid ester ultraviolet-proof finishing agent standard substances into standard stock solutions with the concentration of about 1000 mu g/mL by using methanol or other suitable solvents (such as acetonitrile); and preparing a proper amount of the standard stock solutions into mixed standard stock solutions with the concentration of about 100 mu g/mL by using corresponding methanol or other suitable solvents (such as acetonitrile) (the concentrations of 7 salicylate ultraviolet-proof finishing agents in the mixed standard stock solutions are consistent).
1.5 standard working solution: the mixed standard stock solutions were formulated with the corresponding methanol or other suitable solvent (e.g., acetonitrile) into gradient standard working solutions (mixed standard working solutions) at concentrations of 0.1. mu.g/mL, 0.3. mu.g/mL, 0.5. mu.g/mL, 0.7. mu.g/mL, and 1.0. mu.g/mL, respectively.
Note: the standard storage solution and the standard working solution are stored at 4 ℃ in a dark place, and the effective periods are 12 months and 3 months respectively.
2 instruments and apparatus
2.1 ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS): an Electrospray (ESI) ion source was provided.
2.2 ultrasonic generator: the operating frequency was 40 kHz.
2.3 analytical balance: the sensory amounts are 0.0001g and 0.01 g.
2.4 extractor: screw capped glass tube, 50 mL.
2.5 rotary vacuum evaporator.
2.6 organic phase filtration membrane: 0.22 μm.
Example 1, a liquid chromatography-tandem mass spectrometry detection method for salicylate ultraviolet-proof finishing agents in textiles, which sequentially comprises the following steps:
1) preparing a sample solution to be tested
(1) Taking the textile to be detected, shearing the textile to be detected into small pieces of 5mm multiplied by 5mm, and uniformly mixing;
(2) weighing 1.0g of the sheared sample, accurately weighing to 0.01g, placing in a glass extractor with a screw cap, adding 20mL of methanol to immerse all samples in liquid, sealing the extractor, and ultrasonically extracting in an ultrasonic generator with the working frequency of 40kHz for 30 min;
the material-liquid ratio of the sample to be detected to the extracting agent is as follows: 1g/20 mL;
(3) cooling to room temperature, filtering with 0.22 μm filter head, sealing the obtained filtered sample liquid in a sample bottle for qualitative and quantitative analysis by ultra performance liquid chromatography-tandem mass spectrometer;
2) preparing a standard solution
(1) Preparing 7 salicylic acid ester ultraviolet-proof finishing agent standard substances into standard stock solutions with the concentration of about 1000 mu g/mL by using methanol respectively;
(2) preparing a proper amount of the standard stock solution into a mixed standard stock solution with the concentration of about 100 mu g/mL by using methanol;
(3) preparing the mixed standard stock solution into gradient standard working solutions with the concentrations of 0.1 mu g/mL, 0.3 mu g/mL, 0.5 mu g/mL, 0.7 mu g/mL and 1.0 mu g/mL respectively by using methanol;
3) injecting the gradient standard solution into an ultra-high performance liquid chromatography-tandem mass spectrometer, determining the peak position of each salicylate ultraviolet-proof finishing agent in a positive and negative ion Multiple Reaction Monitoring (MRM) mode, recording the peak area of a quantitative ion pair, and making a standard curve equation by taking the concentration as a horizontal coordinate and the peak area as a vertical coordinate. The method comprises the following specific steps:
(1) the liquid chromatography conditions were:
(A) a chromatographic column: acquity
BEH C18100mm × 2.1mm, 1.7 μm chromatography column or equivalent;
(B) column temperature: 40 ℃;
(C) sample introduction volume: 5 mu L of the solution;
(D) the mobile phase consists of water (mobile phase A) and acetonitrile (mobile phase B); the gradient elution procedure is shown in table 3:
TABLE 3 liquid chromatogram mobile phase elution gradient chart
| Time (min) | Water (%) | Acetonitrile (%) | Flow rate (mL/min) | Type of |
| 0 | 80 | 20 | 0.3 | initial |
| 2 | 20 | 80 | 0.3 | 6 |
| 4 | 20 | 80 | 0.3 | 6 |
| 6 | 80 | 20 | 0.3 | 1 |
(2) The mass spectrum conditions are as follows:
(A) an ion source: an electrospray ion source;
(B) the detection mode is as follows: positive ion Multiple Reaction Monitoring (MRM) mode;
(C) capillary voltage: 3KV (negative ions);
(D) ion source temperature: 120 ℃;
(E) the temperature of desolventizing gas is 380 ℃;
(F) desolventizing air flow rate: 600L/h;
(G) taper hole blowback air flow rate: 50L/h;
(H) other mass spectral conditions are seen in table 2.
When the concentration of the liquid chromatogram-tandem mass spectrometry method disclosed by the invention is 0.1, 0.3, 0.5, 0.7 and 1.0 mu g/mL, the linear relation of 7 salicylic acid ester ultraviolet-proof finishing agents is better, and the table 4 shows.
Table 4. determination of linear equation and linear correlation coefficient of 7 salicylate ultraviolet-proof finishing agents by liquid chromatography-tandem mass spectrometry
4) Measuring 7 salicylate ultraviolet-proof finishing agents in the sample solution to be measured by the filtered sample solution obtained in the step 1) according to the method in the step 3) (namely 5 mu L of filtered sample solution is used for replacing 5 mu L of gradient standard solution, and the balance is equal), and obtaining the content of the 7 salicylate ultraviolet-proof finishing agents in the sample solution by utilizing the established standard curve (linear equation); and obtaining the content of 7 salicylic acid ester ultraviolet-proof finishing agents in the sample to be detected according to the sample dilution multiple (namely the conversion relation between 1g of the sample and the supernatant).
5) Qualitative analysis of the sample
Corresponding to the step 4), under the same test condition, the substance to be detected in the sample has the same retention time with the standard substance detected at the same time, the tolerance of the retention time is +/-0.1 min, the relative abundance of the qualitative ions of the sample is compared with the relative abundance of the corresponding qualitative ions in the standard solution spectrogram with approximate concentration, and if the deviation does not exceed the range specified in the table 5, the corresponding substance to be detected in the sample can be judged.
TABLE 5 maximum permissible deviation of relative ion abundance in qualitative confirmation
| Relative ion abundance,% | ＞50 | ＞20～50 | ＞10～20 | ≤10 |
| Maximum deviation allowed% | ±20 | ±25 | ±30 | ±50 |
6) Quantitative analysis of the sample
Corresponding to the step 4), the method adopts an external standard method for quantification, selects standard working solution with similar concentration according to the content of the measured substance in the sample liquid, inserts equal-volume reference of the standard working solution and the sample liquid into the sample for measurement, and the response values of 7 salicylic acid ester ultraviolet-proof finishing agents in the standard working solution and the sample liquid to be measured are within the linear range of the instrument.
Note 1: if the detection response value of the sample liquid is beyond the linear range detected by the instrument, the sample liquid can be properly diluted and then measured.
Note 2: under the chromatographic conditions, the total ion flow chromatogram of the ultra-high performance liquid chromatography-tandem mass spectrometry of the 7 salicylate ultraviolet-proof finishing agents and the corresponding multi-reaction ion monitoring mass spectrograms are shown in fig. 1, 2-5.
7) Detection lower limit
The lowest detection concentration is determined by 3 times of signal-to-noise ratio (S/N is 3), the lowest quantitative concentration is determined by 10 times of signal-to-noise ratio (S/N is 10), and the determination limit of the method on the liquid chromatography method suitable for detecting 7 salicylate ultraviolet-proof finishing agents in textiles is shown in table 4.
And respectively adding standard mixed solutions of 7 salicylate ultraviolet-proof finishing agents into the blank polyester sample, wherein the adding concentrations are 1mg/kg, 5mg/kg and 10mg/kg respectively, each concentration is set to be 6 times, and the adding recovery rate of the 8 salicylate ultraviolet-proof finishing agents in the blank polyester sample is determined according to the pretreatment and analysis method, and is shown in table 6.
TABLE 6 recovery and relative standard deviation of different concentrations of salicylate anti-UV finish added to blank Terylene samples (n ═ 6)
Several ultraviolet-proof clothing samples randomly extracted in a laboratory are extracted, concentrated and subjected to constant volume according to the operation steps, each sample is parallel for 6 times, and the measurement is carried out by using an ultra performance liquid chromatography-tandem mass spectrometry method, so that the measurement results of the obtained samples are shown in table 7.
TABLE 7 results of actual sample measurement
ND: indicating no detection.
And (3) verification test: the "sample 1# sample 2# sample 3# sample 4 #" described in the above example 2 was detected by the currently recognized high performance liquid chromatography with high detection accuracy, and the results were respectively: 168.1mg/kg of resorcinol monobenzoate was detected in sample No. 1, 158.3mg/kg of phenyl salicylate was detected in sample No. 2, 178.5mg/kg of resorcinol monobenzoate was detected in sample No. 3, and 159.8mg/kg of salicylic acid-p-tert-butylphenyl salicylate was detected in sample No. 4.
Comparative example 1, the "liquid chromatography-tandem mass spectrometry" of step 3) of example 1 was changed to mass spectrometry conditions:
(A) an ion source: an electrospray ion source;
(B) the detection mode is as follows: positive ion Multiple Reaction Monitoring (MRM) mode;
(C) capillary voltage: 3KV (negative ions);
(D) ion source temperature: 100 ℃;
(E) the temperature of desolventizing gas is 300 ℃;
(F) desolventizing air flow rate: 500L/h;
(G) taper hole blowback air flow rate: 50L/h;
the rest is equivalent to embodiment 1.
Comparative example 2, the "gradient elution procedure of mobile phase" of step 3) of example 1 was changed to:
mobile phase A: 0.1% formic acid; mobile phase B: acetonitrile; gradient elution procedure: 0-2 min, 70-20% of A; 2-4 min, 20% A-20% A; 4-6 min, 20-70% of A.
The rest is equivalent to embodiment 1.
All the above comparative examples were examined as described in experiment 1, only setting the addition concentration to 10mg/kg, and the results obtained were compared with those of example 1 as described in the following 8.
Table 8, results of measurement of examples and comparative examples
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (4)
1. The LC-MS detection method of the textile salicylate ultraviolet-proof finishing agent is characterized by comprising the following steps:
1) preparing a sample solution to be detected:
shearing a sample to be detected, adding an extracting agent for ultrasonic extraction, cooling the obtained extracting solution to room temperature, and filtering by using a 0.20-0.45 mu m filter head to obtain a sample solution to be detected;
2) preparing a standard solution:
dissolving 7 salicylic acid ester ultraviolet-proof finishing agents with organic solvents according to the same concentration to form a mixed standard working solution;
performing gradient dilution on the mixed standard working solution to form a gradient standard working solution;
the 7 salicylic acid ester ultraviolet-proof finishing agents comprise: phenyl salicylate, p-tert-butylphenyl salicylate, p-tert-octylphenyl salicylate, resorcinol monobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, 2-ethylhexyl salicylate and trimethylcyclohexyl salicylate;
3) injecting the gradient standard working solution into a liquid chromatogram-tandem mass spectrometer, measuring in a positive and negative ion multi-reaction monitoring mode, determining the peak position of 7 salicylic acid ester ultraviolet-proof finishing agents, recording the peak area of a quantitative ion pair, and making a standard curve equation by taking the concentration as a horizontal coordinate and the peak area as a vertical coordinate;
firstly, the liquid chromatography conditions are as follows:
the mobile phase consists of acetonitrile and water; the gradient elution procedure was: mobile phase A: water; mobile phase B: acetonitrile; gradient elution procedure: 0-2 min, 80-20% of A; 2-4 min, 20% A-20% A; 4-6 min, 20-80% of A; flow rate: 0.2-0.8 mL/min; column temperature: 20-45 ℃; sample introduction volume: 1-10 mu L;
the liquid chromatographic column comprises: acquity
BEH C18100mm × 2.1mm, 1.7 μm chromatography column or equivalent;
secondly, mass spectrum conditions for detecting the liquid chromatogram-tandem mass spectrum are as follows:
the ion source is an electrospray ion source; the detection mode is a positive and negative ion multi-reaction monitoring mode; the capillary voltage is 2-4 kV; the temperature of the ion source is 80-150 ℃; the temperature of the desolventizing gas is 150-380 ℃; the desolventizing air flow rate is 200-800L/h; the flow speed of the cone hole back blowing air is 10-60L/h; the residence time of the ions is 0.03-0.2 s; the voltage of the taper hole is 10-40V; the collision voltage is 5-30V;
the quantitative ion pair of phenyl salicylate is 213.1 to 169.09, the qualitative ion pair is 213.1 to 107.15, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of resorcinol monobenzoate is 213.24-169.2, the qualitative ion pair is 213.24-121.04, and the monitoring mode of negative ion multiple reaction is adopted;
the quantitative ion pair of the salicylic acid-p-tert-butyl phenyl ester is 269.6-149.155, the qualitative ion pair is 269.6-225.35, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the p-dimethylaminobenzoic acid-2-ethylhexyl ester is 278.55>151.13, the qualitative ion pair is 278.55>166.21, and the positive ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the salicylic acid-2-ethylhexyl ester is 249.47>136.99, the qualitative ion pair is 249.47>92.98, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the trimethyl cyclohexyl salicylate is 261.3 to 136.99, the qualitative ion pair is 261.3 to 92.99, and the negative ion multi-reaction monitoring mode is adopted;
the quantitative ion pair of the salicylic acid-p-tert-octylphenyl ester is 325.29-205.44, the qualitative ion pair is 325.29-281.31, and the negative ion multi-reaction monitoring mode is adopted;
4) and taking the sample solution to be detected obtained in the step 1) to determine peak areas of 7 salicylic acid ester ultraviolet-proof finishing agents in the sample solution to be detected according to the method in the step 3), and calculating according to the standard curve equation obtained in the step 3) to obtain the content of the 7 salicylic acid ester ultraviolet-proof finishing agents in the sample to be detected.
2. The LC MS test method for textile salicylate UV-protective finishing agent according to claim 1, characterized by: the organic solvent in the step 2) is methanol or acetonitrile; the extracting agent in the step 1) is methanol or acetonitrile;
and the organic solvent in step 2) is the same as the extractant in step 1).
3. The LC MS detection method for textile salicylate UV-protective finishing agent according to claim 2, characterized in that the step 1) is:
1.1) cutting a sample to be detected into small pieces of 5mm multiplied by 5mm to be used as a sample;
1.2) putting the sample and the extractant into an extractor together according to the material-liquid ratio of 1 g/10-50 mL, sealing the extractor, and performing ultrasonic extraction at room temperature for 10-60 min.
4. The LC-MS detection method for textile salicylate UV-blocking finishing agents according to any one of claims 1 to 3, wherein the step 1) is:
gradient standard working solutions with the concentrations of the salicylate ultraviolet-proof finishing agent respectively being 0.1 mu g/mL, 0.3 mu g/mL, 0.5 mu g/mL, 0.7 mu g/mL and 1.0 mu g/mL are set.
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