CN101699255A - Novel method for separating/enriching trace roxithromycin in environment - Google Patents

Abstract

The invention provides a novel method for separating/enriching trace roxithromycin in environment. The method comprises the following steps: adding 0.4mg.mL<-1> researched roxithromycin test solution in a mouth polished colorimetric tube, wherein the volume of the roxithromycin test solution accounts for 1/50 of total volume of total solution in sublation; adding solid salt to adjust the ionic strength of the solution, shaking the solution to ensure that the solution can be sufficiently dissolved, and adjusting pH to be between 10.8 and 11.8, wherein the salt is solid salt of Na2CO3, (NH4)2SO4, NaH2PO4, MgSO4, Na2SO3 and NaOH; transferring the solution into a sublation column, adding the sublation solvent ionic liquid [Bmim]BF4 into the sublation column, and bringing to total volume by adding water, wherein the volume of the ionic liquid [Bmim]BF4 accounts for 1/25 of total volume of total solution in sublation, and the sublation flow rate of N2 is between 5 and 25mL.min<-1>; floating for 5 to 60 minutes, standing for 1 minute after aeration is stopped; taking out upper enriched [Bmim]BF4 phase by a burette when no air bubble exists; adding a certain amount of 75 percent sulphuric acid and 12 to 19 mL/mg of ROX into the sublation column to perform a color development reaction at room temperature for 0 to 70 minutes; analyzing and determining the content of the solution by using a molecule fluorescence photometry in 350nm excitation wavelength and 508nm emission wavelength. The method optimizes the best condition of sublation, and carries out separation/enrichment analysis on the trace roxithromycin in an actual environmental water sample by combining the molecule fluorescence photometry under an optimized testing condition.

Description

The new method of trace roxithromycin in a kind of separation/enrichment environment

Technical field

The present invention relates to the method for trace roxithromycin in a kind of separation/enrichment environment (ROX), refer in particular to 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid ([Bmim] BF ₄) be flotation agent, with the salting-out agents of sodium carbonate, at inert gas N as phase-splitting ₂Effect under based on ionic liquid aqueous two-phase air-float solvent floatation method (Ionic liquid aqueous two-phase solventsublation, the ILATSS) method of trace roxithromycin in the separation/enrichment environment.

Background technology

Medicine and human health care's product (Pharmaceuticals and personal care products, PPCPs) the environmental exposure problem of pollutant gets more and more people's extensive concerning day by day, wherein antibiotics aquaculture, agricultural and clinical in a large amount of uses, make analysis, migration, the resistance of residual antibiotic in the environment and the problem of aspects such as human and biocenological influence become the focus of environmental ecology scholar and the research of Environmental Analytical Chemistry man.Roxithromycin is a kind of semisynthetic, and its antimicrobial spectrum of macrolide antibiotics of new generation is similar with erythromycin.Because (water body, soil, food etc.) antibiotic residual quantity has popularity, persistence, harmfulness in the environment, set up that separation/beneficiation technologies and detection method are very necessary accordingly.

The most important link of sample analysis is the pre-treatment of sample, and it has material impact to reliability, the accuracy of analytical approach.Measured object concentration is low, component is complicated, chaff interference is many because environmental sample has, so generally all will just can carry out assay determination through pre-treatment.Except that classic methods such as extraction, new pre-treating method also occurs in succession, as Solid-Phase Extraction, supercritical fluid extraction, micro-wave digestion, liquid film separation, accelerated solvent extraction etc.But these methods all have certain scope of application, and it is few to handle sample size, the cost costliness.

Ionic liquid aqueous two-phase extraction (Ionic liquid aqueous two-phase extraction, ILATPE) adopt green hydrophilic ionic-liquid to substitute superpolymer and form double-aqueous phase system, compare with traditional aqueous two-phase extraction, advantages such as the ionic liquid aqueous two-phase extraction has phase-splitting time weak point, extraction process is difficult for emulsification and ionic liquid is environmentally friendly, can recycle, these advantages have just overcome the shortcoming of traditional double aqueous phase system.But the same with aqueous two-phase extraction, still be difficult to overcome the low technology of enrichment multiple " bottleneck ".

Sebba proposed solvent floatation (Solvent Sublation, be called for short SS) first in 1962, be meant a certain amount of nonpolar, low pole or mixed organic solvents are added in the top layer for the treatment of flotation solution, directly with the supreme phase of object flotation.Compare with conventional separation method, have that simple equipments, simple to operate, concentrating and separating are fast, enrichment multiple height (reaches 10 usually ⁴), power consumption characteristics such as low, be particularly useful for handling the trace constituent in a large amount of samples and the separation and concentration extremely dilute solution.

Summary of the invention

The present invention is for overcoming air-float solvent floatation benzene commonly used in the prior art, toluene, dimethylbenzene, isoamylol etc. are made the flotation solvent, can cause secondary pollution to environment, and the deficiency that influences accuracy owing to solvent volatility and ionic liquid aqueous two-phase extraction efficient (enrichment multiple with compare relevant) are limited, the enrichment multiple can only reach 1～2 order of magnitude, the ultratrace example enrichment is needed deficiencies such as repeatedly extraction, a kind of new separation/enrichment method (Ionic liquid aqueous two-phase solvent sublation has been proposed, ILATSS), this method collection ionic liquid aqueous two-phase extraction and air-float solvent floatation are one, its enrichment multiple height, high selectivity, component in detachment process with compare irrelevant, nontoxic, pollution-free, good separating effect, selectivity is good, can handle a large amount of low concentration components simultaneously and have equipment simple, characteristics such as easy and simple to handle.

Technical solution of the present invention

Roxithromycin in the ionic liquid aqueous two-phase air-float solvent floatation method separation/enrichment environment is with nontoxic, free of contamination " green solvent " ionic liquid [Bmim] BF ₄Replace traditional organic solvent and polymerization as extraction solvent, as salting-out agents, utilize inert gas N with the sodium carbonate of cheapness ₂Roxithromycin is separated/method of enrichment.

Concrete steps of the present invention:

(1) in the ground color comparison tube, adds 0.4mgmL ^-1The Roxithromycin test solution that is studied is when wherein the volume of Roxithromycin test solution accounts for flotation 1/50 of total overall solution volume;

(2) ionic strength of adding solid salt regulator solution, vibration is fully dissolved it, regulates pH=10.8～11.8; Wherein said salt is Na ₂CO ₃, (NH ₄) ₂SO ₄, NaH ₂PO ₄, MgSO ₄, Na ₂SO ₃, the NaOH solid salt;

(3) above-mentioned solution is transferred in the columned pneumatic flotation machine, adds flotation lyate ion liquid [Bmim] BF ₄, add water and be settled to cumulative volume; Ionic liquid [Bmim] BF wherein ₄Volume when accounting for flotation total overall solution volume 1/25, N ₂The flotation flow velocity is 5-25mLmin ^-1, flotation 5-60min stops ventilation and left standstill 1 minute, pipettes out the upper strata with dropper when waiting not have bubble and is rich in [Bmim] BF ₄Phase adds a certain amount of 75% sulfuric acid, 12～19mL/mgROX, and color development at room temperature reaction 0-70min, at excitation wavelength 350nm, emission wavelength 508nm place analyzes its content of mensuration with the molecular fluorescence photometry;

(4) optimize the top condition of flotation;

(5) under optimal experimental conditions binding molecule fluorophotometric method to the separation/enrichment analysis of trace roxithromycin in the actual environment water sample.

This method compare with the ionic liquid aqueous two phase extraction technique have the enrichment multiple big, can handle simultaneously that a large amount of samples, selectivity are good, nontoxic, pollution-free, good separating effect, cost be low, and have equipment simple, highly sensitive, measure fast, characteristics such as the extract aftertreatment is easy.

Description of drawings

The different salt consumptions of Fig. 1 are to [Bmim] BF ₄The influence of aqueous two-phase phase-splitting

Wherein: ((a) Na ₂CO ₃(b) Na ₂SO ₃(c) (NH ₄) ₂SO ₄((d) NaH ₂PO ₄)

Fig. 2 sulfuric acid consumption is to the influence of ROX color reaction

Fig. 3 color reaction time is to the influence of ROX photoluminescent property

Fig. 4 RTIL/H ₂The O ratio is to the influence of ROX flotation rate

Fig. 5 salting-out agents Na ₂CO ₃Addition is to the influence of ROX flotation rate

Fig. 6 pH value of solution is to the influence of ROX flotation rate

Fig. 7 flotation time is to the influence of ROX flotation rate

Fig. 8 flotation flow velocity is to the influence of ROX flotation rate

Embodiment:

1) selection of salting-out agents: for [Bmim] BF ₄The ionic liquid aqueous two-phase, The effects Na ₂CO ₃, (NH ₄) ₂SO ₄, NaH ₂PO ₄, MgSO ₄, Na ₂SO ₃, NaOH, Na ₃PO ₄, Na ₂HPO ₄, K ₂HPO ₄, NH ₄Cl, CH ₃COONa, NaNO ₃, NaCl and KCl are to [Bmim] BF ₄Ionic liquid aqueous two-phase phase separation ability is seen Fig. 1.Divide phase time aqueous solution volume 50mL, ionic liquid [Bmim] BF ₄2mL, i.e. V _H2O: V _{[Bmim] BF4}=25: 1.Experiment shows: add a certain amount of Na ₂CO ₃, (NH ₄) ₂SO ₄, NaH ₂PO ₄, MgSO ₄, Na ₂SO ₃, NaOH can make [Bmim] BF ₄The phase-splitting of ionic liquid aqueous two-phase.

2) color reaction: thus this experiment is adopted the sulfuric acid chromogenic reaction to make to be had fluorescence by flotation to the ROX solution that is rich in phase on the ionic liquid and is carried out fluorescent spectroscopy.Along with the increase of 75% sulfuric acid consumption, as shown in Figure 2, fluorescence intensity (20.12a.u～292.5a.u) increase gradually; When its concentration is 18mL/mgROX, this moment fluorescence intensity to be that 297.15a.u reaches maximum, be 18mL/mgROX so this experiment adds 75% sulfuric acid amount when the sulfuric acid chromogenic reaction.(0～70min) growth, (35.33a.u's fluorescence intensity of ROX～149.45a.u) strong more tends towards stability color reaction at last, sees Fig. 3 along with the time.When the color reaction time was 40min, the fluorescence intensity maximum was so the color reaction time of this experimental selection sulfuric acid is 40min.

3) reduce the viscosity of il choice of Solvent: the character that ion liquid density is big, viscosity is high makes it can not be directly used in air-float solvent floatation.Experiment shows, when with H ₂O is better as reducing the viscosity of il effect, and water is to clean the solvent that is easy to get.Work as H ₂O and [Bmim] BF ₄Ratio be 0.2: 1～1.8: 1 o'clock, as Fig. 4, fluorescence intensity increases afterwards earlier and reduces (0～420a.u～0).So this experimental selection adds V _RTIL: V _H2O=1: 1 H ₂O is as the solvent that reduces ion liquid viscosity.

4) flotation conditions optimization:

A) the salting-out agents addition is to the influence of ROX flotation rate

Experimental selection Na ₂CO ₃As [Bmim] BF ₄The salting-out agents of aqueous two-phase, the salting-out agents Na of adding ₂CO ₃Be 0.22g/mL～0.34g/mL, the flotation rate of Roxithromycin increases and tend towards stability at last (65.33%～84.6%) gradually, sees Fig. 5, works as Na ₂CO ₃Volume fraction when being 0.32g/mL, it is maximum 84.6% that flotation this moment rate reaches, so selection Na ₂CO ₃Volume fraction be 0.32g/mL.

B) pH value of solution is to the influence of ROX flotation rate

The effects the influence of pH=10.8～11.8 pair ROX flotation rates, as shown in Figure 6, along with pH increases, the flotation rate of Roxithromycin slightly descends after increasing (47.01%～84.5%) gradually, when pH=11.5, flotation this moment rate reaches maximum 84.5%, so the pH of this experimental selection flotation ROX mother liquor is 11.5.

C) flotation time is to the influence of ROX flotation rate

It is the influence of 5～60min to ROX flotation rate that flotation time has been discussed, as seen from Figure 7, along with the growth of flotation time, the flotation rate of Roxithromycin increases (65%～85.9%) gradually and tends towards stability, when flotation time was 50min, the flotation rate of ROX reached maximal value 85.9%.So this experimental selection flotation time is 50min.

D) the flotation flow velocity is to the influence of ROX flotation rate

The effects N ₂The air supporting flow velocity is 5～25mLmin ^-1Influence to ROX flotation rate.As seen from Figure 8, along with the increase of flotation flow velocity, the flotation rate of Roxithromycin slightly descends after increasing (79.54%-85%) gradually, when the air supporting flow velocity is 15mLmin ^-1The time, the flotation rate of ROX reaches maximal value 85.9%, so this experimental selection flotation flow velocity is 15mLmin ^-1

5) actual sample analysis

Under above-mentioned optimized experiment condition, this experiment is analyzed actual sample in the environment.Get the water sample of four different regions respectively: well water, Yangtze River Water, pond water, jade belt river.Filter, add acid and concentrate, refrigerate in 0 ℃ in order to using.When carrying out sample analysis, add the ROX titer (0.05～0.3mgmL of a certain amount of variable concentrations respectively ^-1) in the above-mentioned water sample of handling well, under best flotation conditions, carry out flotation analysis by technical scheme.Test findings sees Table 1.

Table 1 sample analysis

Claims (1)

1. the new method of trace roxithromycin in the separation/enrichment environment is characterized in that carrying out according to following step:

(1) in the ground color comparison tube, adds 0.4mgmL ^-1The Roxithromycin test solution that is studied is when wherein the volume of Roxithromycin test solution accounts for flotation 1/50 of total overall solution volume;

(2) ionic strength of adding solid salt regulator solution, vibration is fully dissolved it, regulates pH=10.8～11.8; Wherein said salt is Na ₂CO ₃, (NH ₄) ₂SO ₄, NaH ₂PO ₄, MgSO ₄, Na ₂SO ₃, the solid salt of NaOH;

(3) above-mentioned solution is transferred in the columned pneumatic flotation machine, adds flotation lyate ion liquid [Bmim] BF ₄, add water and be settled to cumulative volume; Ionic liquid [Bmim] BF wherein ₄Volume when accounting for flotation total overall solution volume 1/25, N ₂The flotation flow velocity is 5-25mLmin ^-1, flotation 5-60min stops ventilation and left standstill 1 minute, pipettes out the upper strata with dropper when waiting not have bubble and is rich in [Bmim] BF ₄Phase adds a certain amount of 75% sulfuric acid, 12～19mL/mgROX, and color development at room temperature reaction 0-70min, at excitation wavelength 350nm, emission wavelength 508nm place analyzes its content of mensuration with the molecular fluorescence photometry;

(4) optimize the top condition of flotation;

(5) under optimal experimental conditions binding molecule fluorophotometric method to the separation/enrichment analysis of trace roxithromycin in the actual environment water sample.

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