CN101995442A - Method for determining PPCPs (Pharmaceutical and Personal Care Products) in water by LPME (Liquid-phase Micro Extraction) technology - Google Patents
Method for determining PPCPs (Pharmaceutical and Personal Care Products) in water by LPME (Liquid-phase Micro Extraction) technology Download PDFInfo
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Abstract
The invention discloses a method for determining PPCPs (Pharmaceutical and Personal Care Products) in water by an LPME (Liquid-phase Micro Extraction) technology based on ionic liquid, wherein green solvent ion liquid takes the place of the traditional organic solvent, the PPCPs in environmental samples are extracted and separated by utilizing a single drop liquid phase micro extraction technology, and then the samples are detected by the high-performance liquid chromatography. The invention has the characteristics of small environmental pollution, good extraction effect, simple operation, low cost, easy combination with a chromatogram system and the like.
Description
Technical field
The invention belongs to field of environment protection, relate to the method for medicine and personal-care supplies (PPCPs) in a kind of mensuration water.
Background technology
Environmental sample is the matrix complexity often, and disturbing factor is a lot of when directly analyzing, and the concentration of target analytes is very low again, need realize the separation and the enrichment of object by pre-service, thereby satisfies the requirement of corresponding analysis Instrument measuring.Pre-service is the vital link of Analysis of environmental samples process, is directly connected to the accuracy of measurement result.Traditional environmental sample preconditioning technique as liquid-liquid extraction method, soxhlet extraction, often needs to consume a large amount of volatile poisonous organic solvents, the disposal cost height, both be unfavorable for the healthy of researchist, also polluted the environment, do not met the theory of sustainable development.
Medicine and personal-care supplies PPCPs have comprised component such as excipient, the antiseptic etc. of medicine for treatment thing, veterinary drug, essence and flavoring agent, cosmetics, opacifier and sun-proof articles, diagnosis, nutritional medicine and some interpolations in it is manufactured.Some PPCPs in environment than difficult degradation and conversion; the half life period of most of PPCPs class materials is not very long; but because a large amount of frequent uses of medicine and daily nursing articles for use; human or animal's drainage; the unreasonable disposal of discarded medicine; reasons such as the imperfection of sewage disposal technology cause it to be introduced in the environment continuously; and presented the phenomenon of " continuing to exist "; PPCPs can produce certain toxic action to biology; as suppress breeding and the growth of microorganism; the activity that suppresses plant chloroplast and enzyme; cause the animal distortion, caused potential risks for the ecosystem and human health.
China is one of drug manufacture and use big country, and the use amount of personal-care supplies is also very big, and in view of this, the level of pollution that detects and estimate PPCPs in the environment has been imperative.
According to present research and application, the preconditioning technique of PPCPs mainly contains liquid-liquid extraction (LLE), Solid-Phase Extraction (SPE), solid-phase microextraction (SPME) and liquid-phase micro-extraction (LPME) in the environmental sample, and wherein SPE is the most frequently used preconditioning technique.Though SPE has higher concentration effect, need a large amount of sample volumes (0.5-2L), and a SPE extraction column can only be used for a The pretreatment, cost is than higher; In addition, this method operating process is loaded down with trivial details, can use a large amount of poisonous organic solvents equally.Solvent-free abstraction technique SPME and slightly soluble agent abstraction technique LPME because of its centralized procurement sample, extract and be enriched in one, have simple to operate fast, characteristics such as enrichment multiple height, environmental friendliness, in the sample pre-treatments of PPCPs, obtained good application.Because the alternative fiber coat kind of SPME limited (commercial coating mainly is PDMS such as hydrophobicity and PA etc.), only be fit to the mensuration (as alkyl phenol etc.) of a few hydrophobicity PPCPs; Easily broken because of the SPME fiber tenderness again, the cost height has limited its widespread use in PPCP measures greatly.With respect to the SPME technology, LPME because of with low cost, can be particularly suitable for the mensuration of water body Semi-polarity and nonpolar PPCPs according to the flexible slective extraction agent of target analytes.
Existing LPME technical measurement PPCPs, select for use the harmful conventional organic solvents of volatility as extractant mostly, because conventional organic solvents density and viscosity are not enough and not strong to the dissolving power of most PPCPs, its accumulation ability to PPCPs is very limited, and how selecting suitable extractant is the key issue that this field need solve.
Summary of the invention
Volatilize easily in order to overcome conventional organic solvents, and the deficiency not strong to the PPCPs extracting power, solve the problem that lacks the PPCPs method in the water environment that quick and precisely to detect at present, the object of the present invention is to provide the analytical approach of PPCPs in a kind of environmental protection, the testing environment apace with low cost, simple to operate: replace traditional organic solvent with the green solvent ionic liquid, on existing basis, use medicine and personal-care supplies in single dropping liquid-phase microextraction technology extraction isolating environment sample to the correlative study of liquid-phase micro-extraction device; And employing high performance liquid chromatography detection technique.
Ionic liquid is a kind of eco-friendly " green " solvent and catalyzer, is meant a kind of ionic compound that is mainly formed by organic cation and the combination of various negative ion, and they at room temperature often exist with liquid form, therefore, are also referred to as ionic liquid at room temperature.Ionic liquid has steam and forces down, and not volatile, viscosity is big, liquid temperature is interval big, and soluble end is wide, Heat stability is good, characteristics such as electrochemical window is wide can well substitute traditional organic solvent in liquid-phase micro-extraction, extract effects such as object thereby reach optimum.Because ionic liquid is a kind of polar solvent, according to the principle of " similar mixing ", it is particularly suitable for the mensuration of polarity PPCPs.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of liquid-phase micro-extraction is measured the method for PPCPs in the water, comprises step:
(1) at first uses the pH regulator agent to regulate the pH value of sample solution, regulate the concentration of salt in the sample solution with inorganic salts;
(2) sample solution is packed in the sample bottle, put into the stirring magneton, the liquid phase sample introduction needle is drawn ionic liquid, passes gland bonnet, and the tubule of horn-like opening on pinhead sleeve can hang drop; Then the sample introduction syringe needle is immersed in the solution in the sample bottle, tighten bottle cap, sample bottle places on the magnetic stirring apparatus, with support injector is fixed;
(3) fix after, promote the injector push rod ionic liquid in the sample introduction needle all released, make ionic liquid form drop at the injector syringe needle, start magnetic stirring apparatus simultaneously;
(4) after the extraction regular hour, close magnetic stirring apparatus, will remain drop and suck back in the injector, take out injector, the suction extractant makes to mix;
(5) directly feed liquor analysis of hplc detection then.
Described salinity is 0～36g/L; Described inorganic salts are sodium chloride, potassium chloride and anhydrous sodium sulfate.
Described pH value farthest is in the pH value of molecular forms non-ionic form for target analytes; For alkaline target analytes, need be alkali condition with pH regulator; For this analyte, then need pH regulator for acid as acidity; For the neutral target analyte, then pH is neutral.Regulating sample solution to a suitable pH value is the key factor that the present invention can bring into play maximum efficiency.Target analytes farthest is in molecular forms and non-ionic form under optimal pH.According to the principle of this liquid-phase micro-extraction, the target analytes that is in molecular forms is extracted in the extractant ionic liquid easily.
Described tubule is polyfluortetraethylene pipe or polypropylene tube.
Described liquid chromatography microsyringe is 10 μ L or 25 μ L, all cleans more than 5 times with methyl alcohol or acetonitrile before each extraction.
Described pH regulator agent is from hydrochloric acid (or sulfuric acid, phosphoric acid), NaOH (or potassium hydroxide) or phosphate buffered solution.
Described stir speed (S.S.) can be regulated between the big as far as possible rotating speed of zero-sum, the maximum (top) speed of big as far as possible rotating speed for injector needle point liquid is come off; The described extraction time is 0～60 minute.
The testing conditions of described high performance liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1.0ml/min; VWD UV-detector and FLD fluorescence detector.
Described sample bottle is brown sample bottle.
Described sample solution and ion liquid volume ratio are 1: 5000～1: 1000.
Described sample solution 15mL is contained in the sample bottle, puts into the stirring magneton, and the ionic liquid that the liquid phase sample introduction needle is drawn 10 μ L passes gland bonnet, and polyfluortetraethylene pipe on pinhead sleeve can more stably hang drop.Then the sample introduction syringe needle is immersed in the solution in the sample bottle, tighten bottle cap, sample bottle places on the magnetic stirring apparatus, with support injector is fixed on certain location.
Described ionic liquid list dropping liquid-phase microextraction device comprises stirring apparatus and support, has the brown sample bottle of 20mL, stirrer, polytetrafluoroethylene (PTFE) pipe and the liquid chromatography microsyringe of seal bottle cap.Brown sample bottle covers the center and bores an aperture, and the liquid phase sample introduction needle can be passed.
The invention has the beneficial effects as follows:
Characteristics such as (1) the present invention adopts ionic liquid as extractant, and it is big that this material has stickiness, not soluble in water therefore can hang the drop of more volume than common organic solvent, and continuable analysis time are longer, have improved the effect of extraction;
(2) ionic liquid of the present invention's employing is a green solvent, and is littler to the pollution of environment than conventional organic solvents;
(3) device of the present invention is simple, and is easy to operate, be easy to clean, and this method miscellaneous part except that extractant is all reusable, and the generation of waste amount is reduced to minimum;
(4) add an amount of inorganic salts (sodium chloride, potassium chloride and anhydrous sodium sulfate) in the sample solution and regulate salinity, can reduce ion liquid dissolving on the one hand, improve the reappearance of analyzing; The extraction of speeding-up ion liquid on the other hand;
(5) analyzing and testing step of the present invention is simple, fast, can realize the express-analysis test of PPCPs.
Description of drawings
Fig. 1 has represented the influence of different extraction times to the object concentration effect;
Fig. 2 has represented the influence of different pH to the object concentration effect.
Embodiment
Embodiment 1
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Sample solution is the mixed solution of sulphadiazine, sulfamerazine, sulfadimidine, 5-methoxysulfadiazine and 5 kinds of sulfanilamide (SN) of cistosulfa of laboratory preparation, and concentration is respectively 1ppm.
(1) with 1% watery hydrochloric acid with sample solution pH regulator to 6.0, do not add sodium chloride solution or solid, the salinity that makes sample solution is 0.
(2) extracting sample solution 15mL is contained in the brown sample bottle, put into the stirring magneton, draw ionic liquid 1-octyl group-3-methylimidazole hexafluorophosphate of 10 μ L, pass gland bonnet with the liquid phase sample introduction needle, polyfluortetraethylene pipe on pinhead sleeve can more stably hang drop.Then the sample introduction syringe needle is immersed in the solution in the sample bottle, tighten bottle cap, sample bottle places on the magnetic stirring apparatus, with support injector is fixed on certain location.
(3) fix after, promote the injector push rod ionic liquid in the sample introduction needle all released, make ionic liquid form drop at the injector syringe needle, start magnetic stirring apparatus simultaneously, stirring rate is 600 rpms.
(4) extraction was closed magnetic stirring apparatus after 20 minutes, because extraction process intermediate ion liquid has certain dissolving, sucked back in the injector and get final product so will remain drop, and the taking-up injector aspirates twice with extractant, makes to mix.
(5) detect by hand sampling feed liquor analysis of hplc then, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 1 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfadimidine | 5-methoxysulfadiazine | Cistosulfa |
| The enrichment multiple | 2.6 | 3.3 | 3.7 | 6.0 | 10.1 |
Embodiment 2
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Sample solution is the mixed solution that sulphadiazine, sulfamerazine, sulfamethoxazole, cistosulfa, sulfamethoxypyridazine and the sulfanilamide (SN) quinoline of laboratory preparation disliked 6 kinds of sulfanilamide (SN) of beautiful jade, and concentration is respectively 1ppm.
(1) watery hydrochloric acid of using concentrated hydrochloric acid and 1% is regulated the concentration of salt in the sample solution to 18g/L with sample solution pH regulator to 3.0 with the NaCl solid.
(2) extracting sample solution 15mL is contained in the brown sample bottle, put into the stirring magneton, draw ionic liquid 1-octyl group-3-methylimidazole hexafluorophosphate of 10 μ L, pass gland bonnet with the liquid phase sample introduction needle, polyfluortetraethylene pipe on pinhead sleeve can more stably hang drop.Then the sample introduction syringe needle is immersed in the solution in the sample bottle, tighten bottle cap, sample bottle places on the magnetic stirring apparatus, with support injector is fixed on certain location.
(3) fix after, promote the injector push rod ionic liquid in the sample introduction needle all released, make ionic liquid form drop at the injector syringe needle, start magnetic stirring apparatus simultaneously, stirring rate is 600 rpms.
(4) behind the extraction 15min, close magnetic stirring apparatus, because extraction process intermediate ion liquid has certain dissolving, suck back in the injector and get final product so will remain drop, the taking-up injector aspirates twice with extractant, makes to mix.
(5) detect by hand sampling feed liquor analysis of hplc then, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 2 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 5.0 | 5.2 | 11.7 | 21.8 | 28.5 | 40.7 |
Embodiment 3
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Watery hydrochloric acid with 1% transfers to 4.5 with pH, and the concentration of using salt in the KCl solid adjusting sample solution is to 36g/L, and other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 3 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 3.1 | 3.4 | 7.6 | 15.3 | 18.6 | 25.8 |
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Watery hydrochloric acid with 1% transfers to 4.5 with pH, and other Step By Conditions are with embodiment 2, and the volume that changes ionic liquid 1-octyl group-3-methylimidazole hexafluorophosphate is 3 μ L, and this moment, the volume ratio of ionic liquid and sample was 1: 5000.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 4 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 1.1 | 1.2 | 2.3 | 4.0 | 5.1 | 6.9 |
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Other Step By Conditions are with embodiment 4, and the volume that changes ionic liquid 1-octyl group-3-methylimidazole hexafluorophosphate is 15 μ L, and the volume ratio that makes ionic liquid and sample solution is 1: 1000.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 4 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 4.8 | 4.8 | 9.5 | 18.8 | 21.8 | 27.5 |
Embodiment 6
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Watery hydrochloric acid with 1% transfers to 4.5 with pH, and the concentration of using salt in the NaCl solid adjusting sample solution is to 36g/L, and other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2, and the extraction time is 5min.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 4 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 2.4 | 2.7 | 6.7 | 7.6 | 8.6 | 9.6 |
Embodiment 7
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Watery hydrochloric acid with 1% transfers to 6.0 with pH, and other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2, and the extraction time is 60min.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 4 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 2.6 | 3.8 | 9.3 | 13.4 | 21.1 | 51.1 |
Embodiment 8
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
With NaOH pH is transferred to 7.0, the extraction time is 15min, and other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 4 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 1.8 | 2.0 | 4.5 | 2.9 | 5.1 | 12.4 |
Embodiment 9
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
With potassium hydroxide pH is transferred to 7.0, the extraction time is 15min, and other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 4 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 2.0 | 1.9 | 4.2 | 2.8 | 4.6 | 11.2 |
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
Dilute sulfuric acid with 1% transfers to 2.0 with pH, and other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 3 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 2.5 | 2.0 | 5.1 | 14.1 | 20.2 | 35.1 |
Embodiment 11
Adopt single dropping liquid-phase microextraction device.
Use ionic liquid [C
8MIM] PF
6(1-octyl group-3-methylimidazole hexafluorophosphate) is as extractant.
With phosphate buffer pH is transferred to 6.0, other Step By Conditions carry out liquid-phase micro-extraction with embodiment 2.
Detect by hand sampling feed liquor analysis of hplc, liquid chromatographic detection result is as shown in table 1.The condition of liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1ml/min; The UV, visible light detecting device detects wavelength and is made as 265nm.
Table 3 liquid chromatographic detection testing result
| Material | Sulphadiazine | Sulfamerazine | Sulfamethoxypyridazine | Cistosulfa | Sulfamethoxazole | Sulfaquinoxaline |
| The enrichment multiple | 3.1 | 3.9 | 8.3 | 7.8 | 11.9 | 21.3 |
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a liquid-phase micro-extraction is measured the method for PPCPs in the water, comprises step:
(1) at first uses the pH regulator agent to regulate the pH value of sample solution, regulate the concentration of salt in the sample solution with inorganic salts;
(2) sample solution is packed in the sample bottle, put into the stirring magneton, the liquid phase sample introduction needle is drawn ionic liquid, passes gland bonnet, and the tubule of horn-like opening on pinhead sleeve can hang drop; Then the sample introduction syringe needle is immersed in the solution in the sample bottle, tighten bottle cap, sample bottle places on the magnetic stirring apparatus, with support injector is fixed;
(3) fix after, promote the injector push rod ionic liquid in the sample introduction needle all released, make ionic liquid form drop at the injector syringe needle, start magnetic stirring apparatus simultaneously;
(4) after the extraction regular hour, close magnetic stirring apparatus, will remain drop and suck back in the injector, take out injector, the suction extractant makes to mix;
(5) directly feed liquor analysis of hplc detection then.
2. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described salinity is 0～36g/L; Described inorganic salts are sodium chloride, potassium chloride and anhydrous sodium sulfate.
3. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described pH value farthest is in the pH value of molecular forms non-ionic form for target analytes; For alkaline target analytes, need be alkali condition with pH regulator; For this analyte, then need pH regulator for acid as acidity; For the neutral target analyte, then pH is neutral.
4. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described tubule is polyfluortetraethylene pipe or polypropylene tube.
5. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described liquid chromatography microsyringe is 10 μ L or 25 μ L, all cleans more than 5 times with methyl alcohol or acetonitrile before each extraction.
6. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, it is characterized in that: described pH regulator agent is from hydrochloric acid, sulfuric acid, phosphoric acid, NaOH, potassium hydroxide or phosphate buffered solution.
7. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described stir speed (S.S.) is regulated between the big as far as possible rotating speed of zero-sum, the maximum (top) speed of big as far as possible rotating speed for injector needle point liquid is come off; The described extraction time is 0～60 minute.
8. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: the testing conditions of described high performance liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; The moving phase ratio, acetonitrile/water=20/80; The column oven temperature, 25 ℃; Flow velocity is made as 1.0ml/min; VWD UV-detector and FLD fluorescence detector.
9. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described sample bottle is brown sample bottle.
10. liquid-phase micro-extraction according to claim 1 is measured the method for PPCPs in the water, and it is characterized in that: described sample solution and ion liquid volume ratio are 1: 5000～1: 1000.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424501A (en) * | 2011-10-20 | 2012-04-25 | 华南理工大学 | Method for treating trace pharmaceuticals and personal care products (PPCPs) in water through biological activation aeration process |
| CN103033583A (en) * | 2012-12-13 | 2013-04-10 | 江南大学 | Method for enriching and measuring ester components in natural perfume by using ionic liquid |
| CN104535702A (en) * | 2014-12-30 | 2015-04-22 | 天津大学 | Method used for detecting multiple trace drug pollutants in drinking water simultaneously |
| CN104792769A (en) * | 2015-04-09 | 2015-07-22 | 宁波大学 | Dynamic micro-extraction and detection integrated device and method for compounds in aqueous solution sample |
| CN105823837A (en) * | 2016-03-14 | 2016-08-03 | 江苏大学 | Method for detecting phthalate compounds and degradation products thereof in environmental water sample |
| CN106770826A (en) * | 2016-12-22 | 2017-05-31 | 温州医科大学 | A kind of micro-extracting method for detecting triclosan and methyl triclosan |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424501A (en) * | 2011-10-20 | 2012-04-25 | 华南理工大学 | Method for treating trace pharmaceuticals and personal care products (PPCPs) in water through biological activation aeration process |
| CN103033583A (en) * | 2012-12-13 | 2013-04-10 | 江南大学 | Method for enriching and measuring ester components in natural perfume by using ionic liquid |
| CN104535702A (en) * | 2014-12-30 | 2015-04-22 | 天津大学 | Method used for detecting multiple trace drug pollutants in drinking water simultaneously |
| CN104792769A (en) * | 2015-04-09 | 2015-07-22 | 宁波大学 | Dynamic micro-extraction and detection integrated device and method for compounds in aqueous solution sample |
| CN104792769B (en) * | 2015-04-09 | 2017-09-19 | 宁波大学 | The dynamic micro-extraction of compound, detection combined unit and method in aqueous sample |
| CN105823837A (en) * | 2016-03-14 | 2016-08-03 | 江苏大学 | Method for detecting phthalate compounds and degradation products thereof in environmental water sample |
| CN105823837B (en) * | 2016-03-14 | 2018-06-01 | 江苏大学 | The detection method of phthalate compound and catabolite in environmental water sample |
| CN106770826A (en) * | 2016-12-22 | 2017-05-31 | 温州医科大学 | A kind of micro-extracting method for detecting triclosan and methyl triclosan |
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