CN106267898A - Solid-phase micro extraction fiber extraction head and preparation method thereof - Google Patents
Solid-phase micro extraction fiber extraction head and preparation method thereof Download PDFInfo
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- CN106267898A CN106267898A CN201610900350.2A CN201610900350A CN106267898A CN 106267898 A CN106267898 A CN 106267898A CN 201610900350 A CN201610900350 A CN 201610900350A CN 106267898 A CN106267898 A CN 106267898A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Abstract
The present invention proposes a kind of Solid-phase micro extraction fiber extraction head, comprise: a supporting part and an extraction portion, extraction portion comprises an extraction portion corpus fibrosum, it is attached with extraction adsorption layer on extraction portion corpus fibrosum, supporting part comprises a supporting part corpus fibrosum, it is attached with reinforcement coating, extraction portion corpus fibrosum and supporting part corpus fibrosum on supporting part corpus fibrosum to be structure as a whole.The present invention is by improving the structure of Solid-phase micro extraction fiber extraction head, make extraction portion and the supporting part integration of extracting head, in extracting head preparation process, extraction portion and supporting part are exactly an entirety originally, eliminate the extraction portion by extracting head being very difficult in prior art and the interconnective processing step of supporting part, reduce preparation difficulty and the cost of Solid-phase micro extraction fiber extraction head to a great extent.The invention allows for the preparation method of a kind of Solid-phase micro extraction fiber extraction head.
Description
Technical field
The present invention relates to Solid-phase micro extraction fiber extraction head and preparation method thereof.
Background technology
Along with the progress of human society and developing rapidly of science and technology, the productive life of people causes to ecological environment
Serious load.Heavy metal contaminants belongs to persistent pollutant, is not only difficult to degrade, and is entering environment or ecosystem
After can retain, accumulate, convert and circulate, environment once is difficult to administer by the pollution of heavy metal.The toxicity of heavy metal element with
Its morphology is correlated with.Such as: Cr6+The toxicity of (Cr VI) compares Cr3+(trivalent chromium) is much bigger, is easily absorbed by the body and at body
Interior accumulation；Organomercurial toxicity will much bigger more than inorganic mercury, the toxicity with methyl mercury is maximum the most again；Arsenic chemical form can
Being divided into inorganic arsenic and organo-arsenic, inorganic arsenic such as trivalent arsenic and pentavalent arsenic toxicity are very big, but its methylate after then toxicity be substantially reduced；
Selenium is considered as auxotype trace element, but in the various forms of selenium, there is also poisonous and nontoxic dividing ... the most not
Exist in natural water with extremely low content (ng/L rank) with the metallic compound of form, it is possible at different compounds
Mutually convert between form.Therefore, only measure the total amount of element in environment water and can not meet the demand of analysis.Set up element
The high selective morphological analysis method of high sensitivity, be current analytical chemistry important research focus in Environmental Chemistry.Alkane
Base hydrargyrum mainly includes methyl mercury and ethyl hydrargyrum, is the class organo-metallic compound with serious bio-toxicity, its toxic
The strongest is methyl mercury.Famous Japanese minamata disease in 1956, it is simply that because containing hydrargyrum in the waste water of Caustic soda process industry discharge
Ion, is generated methyl mercury by biological methylation process, and is accumulated in vivo by food chain, and concentration is gradually increased,
The nervous system of infringement higher organism causes eventually.Because alkyl mercury belongs to deadly poisonous compound, so its limit value in water body
The lowest.In China's " water environment quality standard " (GB 3838-2002), the limit value of methyl mercury is 1ng/L；Limit in waste water
Value must not be and detected.Two national standard methods that China is existing, pre-treatment step is complicated, needs to make Sulfhydryl Cotton or sulfydryl gauze by oneself,
And amount of samples is big, and use the organic solvent extraction that toxicity is bigger, take time and effort.U.S. EPA 1630, is individually for first
The analysis method of base hydrargyrum, needs to be equipped with capturing device and is combined with atomic fluorescence detector, and the process of analysis is the longest.
Solid-phase microextraction (Solid phase microextraction, SPME) technology be last century the nineties by adding
A kind of Sample Pretreatment Technique that Pawliszyn and Arthur that put on airs proposes first, it is a kind of green solvent-free sample extraction
Take technology, easy and simple to handle, it is achieved that the collection of sample, concentration and sample introduction, and can be with various analytical tool such as gas phase colors in one
Spectrum (GC), high performance liquid chromatography (HPLC), capillary electrophoresis (CE), mass spectrum (MS) and Inductively coupled plasma spectrum (ICP)
Combination, easily realizes automation mechanized operation.
The coating of solid-phase microextraction (SPME) is the core of this technology.The extraction ability of coating is except thing with itself
Outside Physicochemical character is relevant, also closely related with coat preparing technology.Along with the advantage of SPME technology is more and more ground
Studying carefully worker cognitive, the application of SPME is more extensive, various coat preparing technologies such as sol-gel process, Physical coating method,
Epoxy resin fixation, electrochemical deposition method, molecular imprinting method, direct preparation method etc. also obtain development further.
Sol-gel technique be a kind of general, low cost prepare inorganic and organic-inorganic hybrid polymer material
Method, makes one of important method of fiber coat by oneself for laboratory.The preparation condition of sol-gel technique is gentle, coagulating of generation
Glue is stablized, uniformly be can be used to prepare different size, difform fiber material (such as fiber, film, integral material and single dispersing
Granule).
The material of sol gel reaction typically should include at least one presoma, for disperseing the solvent of presoma, catalysis
Agent and water.The poly-condensation and hydrolysis of presoma is the basic reason that homogeneous phase solution is changed into colloidal sol, controls presoma hydrolysis
It is to prepare the premise of high-quality colloidal sol with the condition of polycondensation.The extraction selectivity of sol-gel coating depends primarily on coating
Functional group.Different according to the method introducing functional group, sol-gel coating preparation method can be divided into two kinds: one is straight
Connection, i.e. utilizes organosilane precursor directly to prepare sol-gel coating.This method can pass through two kinds of approach: Yi Zhongshi
Directly utilizing the alkoxy silane with particular functional group, another kind of situation is the self-control alkoxyl silicone containing particular functional group
Alkane.It is bonding method that another kind prepares the method for sol-gel coating, i.e. utilizes that compound self has or passes through chemical modification
Active group on band, reacts with alkoxy silane, functional group is connected on presoma, more anti-by sol-gel
Should be bonded among coating.Between solid-phase micro-extraction coating and the coating prepared due to sol-gel process and coating with quartz
There occurs chemical bonding effect between fiber surface, overcome the caducous shortcoming of coating, reached high temperature resistant, solvent resistant, made
Effect by life-span length.But sol-gel technique also has the shortcoming of himself, and substantial amounts of process variable, such as silylating reagent
With mol ratio, sol solutions pH value, the kind of catalyst and consumption, reaction temperature and time, aging temperature and the ageing time of water,
Organic impurities etc. can affect gel or the aperture of crystal grain and specific surface area so that it is physicochemical characteristic is affected, thus affects conjunction
Become the functional of material.And sol-gel process is still at present prepares coating by the most coated, sol solutions when starting coated
Viscosity, structure, thickness and the uniformity of coating also have a certain impact by the speed that proposes from sol solutions of fiber etc..
The organic metal solid phase micro-extraction technique major part having been reported uses the PDMS (dimethyl-silicon of commercialization 100 μm
Oxygen alkane) coating, for alkyl mercury, repeatability is the poorest.
The extracting head of existing solid-phase microextraction generally comprises an extraction portion, extraction portion using cylindrical fibre as substrate,
Outer surface absorbent coating (i.e. extracts coating), and the one end in extraction portion is fixed to one than cylindrical fibre substrate slightly slightly a bit
Rigid support portion one end on, the other end in this rigid support portion is secured by threads in plunger.Extracting head is contained in hollow
In syringe.When not using, extraction portion is positioned at inside hollow syringe；When needing to use, promoting plunger, the extraction portion translation of drive passes
Hollow syringe, extracts testing sample.Extracting head of the prior art have employed two-piece design extraction portion and combines hard and prop up
Support part, to increase the toughness of whole extracting head, but this considerably increases difficulty by tiny the most also to the preparation of extracting head
Cylindrical fibre substrate be coaxially fixed in rigid support portion need manufacturing process the most accurately, in current world wide only
There is one or two company it is achieved that thus cause extracting head price much more expensive.
Summary of the invention
For solving the deficiency that prior art exists, the present invention proposes a kind of Solid-phase micro extraction fiber extraction head, has and changes
The structure structure entered, it is prepared raw material and is readily obtained, and enables its preparation technology to be greatly simplified.
For reaching above-mentioned purpose, the Solid-phase micro extraction fiber extraction head of the present invention comprises: a supporting part and an extraction portion, extraction
The portion of taking comprises an extraction portion corpus fibrosum, and extraction portion corpus fibrosum is attached with extraction adsorption layer, and supporting part comprises a supporting part fiber
Body, supporting part corpus fibrosum is attached with reinforcement coating, extraction portion corpus fibrosum and supporting part corpus fibrosum and is structure as a whole.
Further, as extracting after one section of one end 1-2cm with the quartz fibre strengthening coating removes and strengthens coating
Portion's corpus fibrosum, other parts of this section of quartz fibre are as supporting part.
Further, strengthening coating is polyimide coating.
Further, extraction portion corpus fibrosum through rough surface and alkaline solution immersion treatment to expose more silanol
Base.
Further, the rough surface of extraction portion corpus fibrosum and alkaline solution immersion treatment are to expose more silanol base
Concretely comprise the following steps: extraction portion corpus fibrosum is immersed corrosion in Fluohydric acid. and carries out rough surface, then at sodium hydroxide solution
Middle immersion is to expose more silanol base.
Further, extraction adsorption layer is polymeric layer, is chemically bound in and processes through rough surface and alkaline solution
Extraction portion corpus fibrosum on.
Further, polymer is formed by following reaction:
It is initially formed OH-PDMS sol-gel solution:
The first step: hydrolysis
Second step: polyreaction
3rd step: OH-PDMS sol gel reaction
Then silanol base and the OH-PDMS sol-gel solution on corpus fibrosum surface, extraction portion carries out bonding reaction, is formed poly-
Compound layer:
The present invention is by improving the structure of Solid-phase micro extraction fiber extraction head so that the extraction portion of extracting head and supporting part one
Body, in extracting head preparation process, extraction portion and supporting part are exactly an entirety originally, and it is the most difficult to eliminate in prior art
With the extraction portion by extracting head completed and the interconnective processing step of supporting part, reduce the micro-extraction of solid phase to a great extent
Take preparation difficulty and the cost of fibre abstraction head.
The invention allows for the preparation method of a kind of Solid-phase micro extraction fiber extraction head, by directly fine to one section of quartz
A part for dimension carries out being roughened, more exposure silanol base and bonding extraction adsorption layer process, and obtains consolidating of integral structure
Phase extraction fibre abstraction head so that the preparation technology of fibre abstraction head is greatly simplified.
The preparation method of the Solid-phase micro extraction fiber extraction head of the present invention comprises:
Step (1): take one section of quartz fibre with reinforcement coating, its one end 1-2cm length is used as preparation extraction portion, will
Reinforcement coating removal in the 1-2cm length of one end forms extraction portion corpus fibrosum, and is carried out slightly by the extraction portion corpus fibrosum exposed
Roughening and alkaline solution immersion treatment expose silanol base with more, clean and dry；
Step (2): preparation OH-PDMS sol-gel solution；
Step (3): the extraction portion corpus fibrosum handled well in step 1 is inserted the OH-PDMS sol-gel solution prepared
In, take out after heating a period of time, now extraction portion corpus fibrosum is bonded with extraction adsorbing material, be dried aging；
Step (4): checking extraction portion, if not reaching requirement, repeating step 3, meeting, until being formed, the extraction adsorption layer required
Thickness.
Further, strengthening coating is polyimide coating.
Further, in step (1), carry out being roughened and alkaline solution immersion treatment by the extraction portion corpus fibrosum exposed
To expose concretely comprising the following steps of more silanol base: extraction portion corpus fibrosum is immersed in Fluohydric acid. and corrodes, then at sodium hydroxide
Solution soaks expose more silanol base.
Further, in step (2), the method preparing OH-PDMS sol-gel solution is: by methyl trimethoxy epoxide silicon
After the poly-dimethoxysiloxane of oxygen alkane, terminal hydroxy group, containing hydrogen silicone oil, trifluoroacetic acid and water mixing, it is placed in ultrasonic cleaner and holds
Continuous ultrasonic, i.e. obtain OH-PDMS sol-gel solution.
Further, the reaction equation preparing OH-PDMS sol-gel solution is:
The first step: hydrolysis
Second step: polyreaction
3rd step: OH-PDMS sol gel reaction
Further, in step (3), extraction adsorbing material is polymer, by OH-PDMS sol-gel solution with through thick
The silanol base on the corpus fibrosum surface, extraction portion that roughening and the more silanol base of exposure process carries out bonding reaction formation, reactional equation
Formula is:
With surface, quartz fibre through acid corrosion is solid-phase micro-extraction fibre carrier to the present invention, in sol gel reaction
Presoma and coating that middle introducing contains hydroxyl fix phase, prepare one layer of extraction adsorption layer by thermal-initiated polymerization, utilize a huge sum of money
Belong to the coordination between hydroxyl and the absorbability of polymer, extract and be enriched with alkyl mercury.
The advantage of Solid-phase micro extraction fiber extraction head prepared by the present invention is as follows:
1, preparation technology is simple, and raw material is easy to get, and process equipment is few；
2, adsorption capacity is high, stable chemical nature；
3, this fibre abstraction head can be used for measuring alkyl mercury in water quality, the most well；
4, detection limit is low, highly sensitive.
5, favorable reproducibility, accuracy is high.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the present invention described further and illustrate.
Fig. 1 is the generalized section of the Solid-phase micro extraction fiber extraction head of first-selection embodiment of the present invention.
Fig. 2 is that the extraction portion scanning electron microscope of the Solid-phase micro extraction fiber extraction head of first-selection embodiment of the present invention characterizes
The photo arrived.
Fig. 3 is by using gas chromatogram-triple by the Solid-phase micro extraction fiber extraction head of first-selection embodiment of the present invention
Quadrupole rod tandem mass spectrometry measures the result figure that in water quality, alkyl mercury (methyl mercury and ethyl hydrargyrum) obtains.
Detailed description of the invention
As it is shown in figure 1, the Solid-phase micro extraction fiber extraction head 1 of the first-selected embodiment of the present invention comprises: extraction portion 11,
Support part 15.Wherein, extraction portion 11 comprises an extraction portion corpus fibrosum 12, is attached with extraction absorption at extraction portion corpus fibrosum 12 outer surface
Layer 14.Supporting part 15 comprises a supporting part corpus fibrosum 16, is attached with reinforcement coating 18 at supporting part corpus fibrosum 16 outer surface.As
One of improvements of the present invention, in this first-selection embodiment, extraction portion corpus fibrosum 12 and supporting part corpus fibrosum 16 are integrated
Structure, i.e. the two is an entirety, after cutting down from a quartz fibre, extraction portion corpus fibrosum 12 and supporting part corpus fibrosum 16 it
Between never fractureed.
When preparing the Solid-phase micro extraction fiber extraction head of the present invention, from a quartz fibre, intercept a quartz fibre
Section, the corpus fibrosum of its one end certain length is used for making extraction portion, and other parts are used for making supporting part.Preferably, for system
Standby easy, the most existing quartz fibre finished product can be used as raw material.Owing to the solid-phase micro-extraction fibre of the present invention extracts
Taking the quartz fibre required for head very thin, diameter of section only has tens to arrive hundreds of μm, is less than 1mm thick, it is easy to lose brokenly
Split, it is therefore desirable to supporting part is improved intensity, it is preferable that the surface-coated at supporting part corpus fibrosum 16 has reinforcement coating 18 to carry
The intensity of high quartz fibre and toughness.In this first-selection embodiment, it is preferable that choose the existing polyamides that is coated with on market sub-
The quartz capillary finished product of amine coating uses.In other embodiments, it would however also be possible to employ surface-coated has other compositions
Strengthen the quartz fibre finished product of coating or additionally coating is strengthened in coating on quartz fibre.
As it is shown in figure 1, the Solid-phase micro extraction fiber extraction head 1 of the first-selected embodiment of the present invention to use surface-coated to have poly-
Imido hollow quartz fibers is prepared from, and therefore its extraction portion 12 also has a hollow hole 13, supporting part has a hollow
Hole 17, wherein hollow hole 13 and hollow hole 17 are interconnected.The preparation method bag of the Solid-phase micro extraction fiber extraction head 1 of the present invention
Containing following steps:
Step (1): take one section of quartz fibre with reinforcement coating, its one end 1-2cm length is used as preparation extraction portion, will
Reinforcement coating removal in the 1-2cm length of this one end forms extraction portion corpus fibrosum, and by coarse for the extraction portion corpus fibrosum that exposes
Change and alkaline solution soaks and exposes silanol base with more, clean and dry；
Step (2): prepare the poly-dimethoxysiloxane of terminal hydroxy group (that is: OH-PDMS) sol-gel solution；
Step (3): the extraction portion corpus fibrosum handled well in step 1 is inserted the OH-PDMS sol-gel solution prepared
In, take out after heating a period of time, now extraction portion corpus fibrosum has been attached with extraction adsorbing material, be dried and make this extraction inhale
Enclosure material is aging；
Step (4): checking extraction portion, if not reaching requirement, repeating step 3, meeting, until being formed, the extraction adsorption layer required
Thickness.
It is shown that after the extraction adsorption layer in extraction portion is prepared as in FIG, the thickness in extraction portion and supporting part thick
Thin consistent, but this be theoretic unanimously, in practical operation, as long as the thickness of the two is more or less the same, i.e. think that the two is thick
Thin consistent, and the most proper just the same, illustrate at this.
In step (1), if strengthening coating is polyimides, can remove by the way of baked wheaten cake, simple and fast；And
In other embodiments, if the reinforcement coating of other materials, need to use corresponding mode to remove.More specifically, will be sudden and violent
The extraction portion corpus fibrosum exposed carries out being roughened and alkaline solution soaks and with the more method exposing silanol base is: will extract portion
Corpus fibrosum immerses in Fluohydric acid. and corrodes, and then soaks to expose silanol base in sodium hydroxide solution.Then clean, room temperature is dried in the air
Dry.Wherein, extraction portion corpus fibrosum being roughened main ground can make its diameter reduce so that in step below
In be prepared for extracting after adsorption layer, extraction portion diameter can free in and out metal coating sleeve.After the roughening, then will extraction
Take portion's corpus fibrosum to soak in alkaline solution so that corpus fibrosum surface, extraction portion exposes more silanol base so that inhale in extraction
After prepared by attached layer, the extracting head repeatability when being used for multiple times is significantly improved.
In step (2), the method preparing OH-PDMS sol-gel solution is: by methyl trimethoxy epoxide siloxanes, end
After the poly-dimethoxysiloxane of hydroxyl (that is: OH-PDMS), containing hydrogen silicone oil, trifluoroacetic acid and water mixing, it is placed in ultrasonic cleaner
Middle continual ultrasonic, i.e. obtains OH-PDMS sol-gel solution.In practical operation, owing to trifluoroacetic acid uses trifluoro second
Acid solution, i.e. trifluoroacetic acid and water, therefore can choose whether also additionally to add water according to the concentration of trifluoroacetic acid solution.Step
(2), in, the equation generating OH-PDMS sol-gel solution is as follows:
The first step: hydrolysis
Second step: polyreaction
3rd step: OH-PDMS sol gel reaction:
In step (3), extraction adsorbing material is polymer, by above-mentioned OH-PDMS sol-gel solution with through coarse
The silanol base on the corpus fibrosum surface, extraction portion of change and alkaline solution immersion treatment carries out bonding reaction formation, and reaction equation is:
In step (4), checking extraction portion refers to test extraction portion, such as, it is carried out dimensional measurement to know
Whether extraction adsorption layer reaches desired thickness or carries out performance test to know whether extraction adsorption layer reaches desired properties.
Performance and its thickness of wherein extracting adsorption layer are directly related.
By improving structure and the preparation technology of Solid-phase micro extraction fiber extraction head, extraction portion and supporting part one are obtained
The Solid-phase micro extraction fiber extraction head changed, eliminates the extraction portion by extracting head and support being very difficult in prior art
The interconnective processing step in portion.
After preparing Solid-phase micro extraction fiber extraction head 1, it is possible to assemble solid-phase micro-extraction fibre device further.Will
The exposed ends epoxy resin of the supporting part with the Solid-phase micro extraction fiber extraction head 1 of extraction adsorption layer is bonded on screw, dry
Dry fixing, Solid-phase micro extraction fiber extraction head 1 is put in metal sleeve, is placed in exsiccator and is dried aging 12h, then to gas phase color
In spectrometer injection port, being dried aging 2h, temperature is gradually increased to 200 DEG C from 60 DEG C.Take out after aging and at room temperature cool down, standby
With.The newest with before, Solid-phase micro extraction fiber extraction head 1 is both needed at 200 DEG C be dried aging 0.5h.
Solid-phase micro-extraction fibre extraction in the first-selected embodiment of the present invention is described below in conjunction with more specifically parameter
The preparation method of head.
Step (1): one section of 1-2cm length with the one end of the quartz fibre strengthening coating is removed and strengthens shape after coating
Become extraction portion corpus fibrosum, and be dipped in 1h in Fluohydric acid. (extraction portion corpus fibrosum roughening), take out after cleaning, first at the hydrogen of 1mol/L
In sodium hydroxide solution, immersion 1h is to expose more silanol base, then cleans, dries standby under room temperature；
Step (2): the preparation of OH-PDMS sol-gel solution: by 300 μ L methyl trimethoxy epoxide siloxanes, 180mg end
After the poly-dimethoxysiloxane of hydroxyl, 30mg containing hydrogen silicone oil, 200 μ L trifluoroacetic acids and the mixing of 10 μ L water, it is placed in ultrasonic waves for cleaning
Continual ultrasonic 30min in device, i.e. obtains OH-PDMS sol-gel solution；
Step (3): the above-mentioned extraction portion handled well is inserted in the OH-PDMS sol-gel solution prepared, heat one
The section time takes out, and heating-up temperature more than 50 DEG C typically takes 50 DEG C-80 DEG C, and the highest reaction of temperature is the fastest, the highest bad control, this
Sample fiber surface just bonding last layer polymer coating (extraction adsorbing material), is dried aging；
Step (4): checking extraction portion, if after checking, the loading capacity of extraction adsorption layer is inadequate, repeats aforesaid operations
Several times until extraction adsorption layer loading capacity meets requirement.Loading capacity meets requirement and i.e. means to extract the thickness of adsorption layer
Reach requirement.
Then, the extraction portion being attached with hydroxy polymer coating is added supporting part epoxy resin and is bonded on screw, fixing
After be contained in metal sleeve, be placed in exsiccator and be dried 12h, then in gas chromatograph injection port, aging 2h, temperature from 60 DEG C by
Edge up to 200 DEG C (slowly heating up).Take out after aging again and cool down under room temperature, standby.The newest with before, all exist
Aging 0.5h at 200 DEG C.
Being characterized by this extraction portion scanning electron microscope, result is as shown in Figure 2.The extraction of alkyl mercury in water quality is carried out with this extraction portion
Taking and be enriched with, use gas chromatogram-triple quadrupole bar tandem mass spectrometry to measure, many reaction monitorings pattern is scanned.Result is such as
Shown in Fig. 3.
With the alkyl mercury standard solution of pure water preparation variable concentrations, concentration range is between 1～80ng/L, first by the present invention
The Solid-phase micro extraction fiber extraction head selecting embodiment carries out extracting, is enriched with, measures, it is thus achieved that result linear relationship good, phase
Close coefficient r >=0.990.
With 7 parts of 0.1ng/L alkyl mercury standard solution of the parallel preparation of pure water, analyze and measure.Specify according to HJ168-2010, meter
Calculate the standard deviation S of 7 parallel assays, according to method detection limit computing formula MDL (method detection limit)=3.143 × S, calculate
The detection limit of the method, methyl mercury is 0.03ng/L, and ethyl hydrargyrum is 0.03ng/L.The method detection limit can meet China earth's surface
The limit value requirement of water and sewage discharge.
Alkyl mercury in water is extracted, is enriched with by the Solid-phase micro extraction fiber extraction head using the present invention, and detection obtains
Preci-sion and accuracy the results are shown in Table 1.Actual sample spiked levels is 0.10,5.00,50.0ng/L, the RSD of methyl mercury is (relatively
Standard deviation) between 3.0～8.2%, the response rate is between 77.8～114.8%；The RSD of ethyl hydrargyrum 5.5～7.2% it
Between, the response rate is between 92.2～114.3%.The relatively data of statistics understand, and make Fluohydric acid. corrosion-hydroxylating poly dimethyl by oneself
The preci-sion and accuracy of siloxane solid phase micro extraction fiber is preferable, can meet the needs of lab analysis.
Table 1
By foregoing description, those of ordinary skill in the art it is readily understood that, first embodiment is adopted
The hollow hole of hollow quartz fibers for the extracting fiber head not contribution of the present invention, in other embodiments, also
Solid quartz fibre can be used.
The preferred embodiment of the present invention is only described by above-mentioned detailed description of the invention, and not guarantor to the present invention
The scope of protecting is defined.On the premise of without departing from design concept of the present invention and scope, those of ordinary skill in the art
According to word provided by the present invention description, accompanying drawing to the various deformation done by technical scheme, substitute and improve,
The protection category of the present invention all should be belonged to.Protection scope of the present invention is determined by claim.
Claims (13)
1. a Solid-phase micro extraction fiber extraction head, comprises: a supporting part and an extraction portion, it is characterised in that described extraction portion
Comprising an extraction portion corpus fibrosum, described extraction portion corpus fibrosum is attached with extraction adsorption layer, described supporting part comprises a supporting part
Corpus fibrosum, described supporting part corpus fibrosum is attached with reinforcement coating, described extraction portion corpus fibrosum and described supporting part corpus fibrosum is
Integrative-structure.
2. Solid-phase micro extraction fiber extraction head as claimed in claim 1, it is characterised in that a section with described reinforcement coating
One end 1-2cm of quartz fibre removes and strengthens after coating as described extraction portion corpus fibrosum, other of described one section of quartz fibre
Part is as described supporting part.
3. Solid-phase micro extraction fiber extraction head as claimed in claim 1, it is characterised in that described reinforcement coating is polyimides
Coating.
4. Solid-phase micro extraction fiber extraction head as claimed in claim 1, it is characterised in that described extraction portion corpus fibrosum is through table
Face roughening and alkaline solution immersion treatment are to expose more silanol base.
5. Solid-phase micro extraction fiber extraction head as claimed in claim 4, it is characterised in that the surface of described extraction portion corpus fibrosum
Roughening and alkaline solution immersion treatment are to expose concretely comprising the following steps of more silanol base: immersed by described extraction portion corpus fibrosum
In Fluohydric acid., corrosion carries out rough surface, then soaks to expose more described silanol base in sodium hydroxide solution.
6. Solid-phase micro extraction fiber extraction head as claimed in claim 4, it is characterised in that described extraction adsorption layer is polymer
Layer, is chemically bound on the described extraction portion corpus fibrosum that rough surface and alkaline solution process.
7. Solid-phase micro extraction fiber extraction head as claimed in claim 6, it is characterised in that described polymer is by following reaction
Formed:
It is initially formed OH-PDMS sol-gel solution:
The first step: hydrolysis
Second step: polyreaction
3rd step: OH-PDMS sol gel reaction
The silanol base on corpus fibrosum surface, the most described extraction portion and OH-PDMS sol-gel solution carry out bonding reaction, form institute
State polymeric layer:
8. a preparation method for Solid-phase micro extraction fiber extraction head, comprises the steps of
Step (1): take one section of quartz fibre with reinforcement coating, its one end 1-2cm length is used as preparation extraction portion, by described
Reinforcement coating removal in the 1-2cm length of one end forms extraction portion corpus fibrosum, and is entered by the described extraction portion corpus fibrosum exposed
Row roughening and alkaline solution immersion treatment expose silanol base with more, clean and dry；
Step (2): preparation OH-PDMS sol-gel solution；
Step (3): the extraction portion corpus fibrosum handled well in step 1 is inserted the described OH-PDMS sol-gel solution prepared
In, take out after heating a period of time, the most described extraction portion corpus fibrosum is bonded with extraction adsorbing material, be dried aging；
Step (4): verifying described extraction portion, if not reaching requirement, repeating step 3, meets, until being formed, the extraction adsorption layer required
Thickness.
9. the preparation method of Solid-phase micro extraction fiber extraction head as claimed in claim 8, it is characterised in that described reinforcement coating
It it is polyimide coating.
10. the preparation method of Solid-phase micro extraction fiber extraction head as claimed in claim 8, it is characterised in that in step (1),
Carry out the extraction portion corpus fibrosum exposed being roughened and alkaline solution immersion treatment specifically walking with the more silanol base of exposure
Suddenly it is: extraction portion corpus fibrosum is immersed in Fluohydric acid. and corrodes, then soak to expose described silanol base in sodium hydroxide solution.
The preparation method of 11. Solid-phase micro extraction fiber extraction head as claimed in claim 8, it is characterised in that in step (2),
The method preparing OH-PDMS sol-gel solution is: by methyl trimethoxy epoxide siloxanes, the poly-dimethoxysiloxane of terminal hydroxy group,
After containing hydrogen silicone oil, trifluoroacetic acid and water mixing, it is placed in continual ultrasonic in ultrasonic cleaner, i.e. obtains OH-PDMS sol-gel
Solution.
The preparation method of 12. Solid-phase micro extraction fiber extraction head as claimed in claim 11, it is characterised in that preparation is described
The reaction equation of OH-PDMS sol-gel solution is:
The first step: hydrolysis
Second step: polyreaction
3rd step: OH-PDMS sol gel reaction
The preparation method of 13. Solid-phase micro extraction fiber extraction head as claimed in claim 12, it is characterised in that in step (3)
Described extraction adsorbing material is polymer, soaks by described OH-PDMS sol-gel solution with through roughening and alkaline solution
The silanol base on the corpus fibrosum surface, described extraction portion processed carries out bonding reaction formation, and reaction equation is:
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