CN101496958B - Solid phase micro-extraction device and method for preparing fibre extraction head thereof - Google Patents
Solid phase micro-extraction device and method for preparing fibre extraction head thereof Download PDFInfo
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Abstract
The invention relates to a solid phase micro-extraction device and a method for preparing a fiber extraction head thereof. The solid phase micro-extraction device comprises a micro sample injector, the inside of a sample injector push rod is provided with a stainless steel capillary pipe, and the lower end of the sample injector push rod is inserted with the fiber extraction head. The preparationmethod for the fiber extraction head comprises: corroding one end of a metal fiber into aqua regia, while corroding the other end in HF; dissolving metal salt and organic ligand in a solvent in a hotwater reaction kettle to obtain a reaction mixed liquor; and immerging the one end of the metal fiber corroded by the HF after pretreatment into the reaction mixed liquor, and controlling the temperature to between 50 and 220 DEG C and the time to between 6 and 90 hours to prepare the solid phase micro-extraction head of which the surface is grown with metal organic porous skeleton materials in situ. The solid phase micro-extraction device has the advantages of difficult damage of extracted fibers, high temperature resistance, low cost, good extraction performance, capability of replacing theextraction head, and large adsorption capacity. The method can grow porous skeleton materials with different structures on the extraction head aiming at different compounds so as to design high-selectivity enrichment to a target object, and has wide application prospect in the aspect of analytical chemistry.
Description
[technical field]: the present invention relates to a kind of assembling of solid-phase micro-extracting device and the preparation of fiber thereof, this fiber is the novel solid phase micro extraction fiber that the surface in situ growth has the organic stephanoporate framework material of metal.
[background technology]: solid phase micro-extraction technique is a kind of sample pretreatment new technology, this method has that to consume solvent few, highly sensitive, advantage such as easily be automated, existing commercialization solid-phase micro-extracting device mainly scribbles chromatographic stationary vitreous silica fibre abstraction head mutually by handle with the surface and forms, usually the vitreous silica fiber is hidden in the syringe needle, can promote the injector push rod when needing quartz fibre is stretched out in syringe needle.This extracting head all is fixing phase coating to be coated with steep on quartz fibre as extracting fiber, these fixedly the phase coating mainly comprise dimethyl silicone polymer (PDMS), polyacrylate (PA), carbon molecular sieve/vinyl benzene (CW/DVB) or carbon molecular sieve/molecular template resin (CW/TPR), polyethylene glycol/dimethyl silicone polymer (CAR/PDMS), but this type coating only is to have covered the polarity scope roughly, the selectivity that has is limited, and this type coating all is the surface that high polymer is fixed on quartz fibre by photocuring or heating means, so mechanicalness and heat endurance are all relatively poor, vitreous silica fibre abstraction head stretches out in the syringe needle of being everlasting and withdrawal is peeled off the coating easy fracture, and the quartz fibre frangibility, the scope of application and the life-span of greatly having limited extracting head.
In order to overcome the shortcoming of quartzy extracting head frangibility, Recent study personnel are devoted to develop various extracting fibers with certain toughness.Research great majority the most widely is particularly stainless steel wire of wire, carries out SPME on its surface by various physicochemical effect coated metal oxides, Bio-sil and other polymer, and has obtained effect preferably.When extraction, dual mode is arranged usually, a kind of is this class extracting head to be fixed in the commercialization solid-phase micro-extracting device extract, but this class device costs an arm and a leg, and need to consider the complex interface problem of metal extraction head and extraction equipment; Another is that wire is inserted in the injection device, and front end of wire extracts all kinds of materials as extracting head by various finishinges.This device has cheap, simple and practical characteristics, and still, owing to use whole wire as extracting fiber, the making of extracting head and replacing are all comparatively complicated.
(Metal Organic Frameworks MOFs) is a kind of porous material of the molecular sieve analog that forms by coordination by metal and organic ligand to the organic stephanoporate framework material of metal.Because this class material has duct rule homogeneous, controllable size, Heat stability is good, characteristics such as specific area is big, and can obtain more suitably hole of performance by regulation and control structure construction unit, thereby allow more rational design and synthetic, aspect sample pretreatment so this class material has broad application prospects.
The property of the organic stephanoporate framework material of metal has determined it to can be used as a kind of good SPME material, but does not have method can realize the growth in situ of the organic stephanoporate framework material of metal in the metal surface so far, can't be applied to SPME.
[summary of the invention]: the objective of the invention is to overcome existing method and technology above shortcomings, provide a kind of novel extraction head removable simple and easy solid-phase micro-extracting device, and the method for the organic stephanoporate framework material of a kind of stainless steel surfaces growth in situ metal is provided, utilizes this method to prepare the metallic fiber extracting head of the organic stephanoporate framework material of surface metallization.
Solid-phase micro-extracting device provided by the invention comprises a microsyringe, and the stainless steel capillary as fiber bodies is installed in the injector push rod, and the lower end of stainless steel capillary is equipped with plug-in type fibre abstraction head.
The internal diameter of described stainless steel capillary is 50-300 μ m, and external diameter is 200-500 μ m, and described fibre abstraction head is that the organic stephanoporate framework material of metal of 30-200 μ m is formed by a stainless steel wire and by the thickness that growth in situ is coated in the stainless steel wire surface; Described microsyringe is the no dead volume microsyringe of conventional gas-chromatography.
The preparation method of the fibre abstraction head described in the above solid-phase micro-extracting device comprises the steps:
The first, the preliminary treatment of stainless steel wire:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the stainless steel wire of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control stainless steel wire external diameter, making corrosion back stainless steel wire external diameter is 0.05-0.20mm, an other end of stainless steel wire is placed HF, and the room temperature corrosion was dried after the pure water rinsing to this section stainless steel wire surface blackening in 20-40 minute;
The second, the stainless steel wire surface in situ prepares the organic stephanoporate framework material of metal:
Put into water or ethanol or N in the hydrothermal reaction kettle, the dinethylformamide solvent, one or more slaines and one or more organic ligands be dissolved in the coordination ratio obtain reaction mixture in the solvent, the pretreated stainless steel wire of the first step is put into this hydrothermal reaction kettle, one end of HF corrosion immerses in the reaction mixture, the control reaction temperature is 50-220 ℃, and reaction time 6-90h makes the grown solid phase micro-extracting head of the organic stephanoporate framework material of metal of surface in situ.
Wherein said slaine is inorganic metal salt copper nitrate, zinc nitrate, iron chloride, aluminum nitrate or chromic nitrate etc.
Described organic ligand is a terephthalic acid (TPA), trimesic acid, triethyl group diamines etc.
The assembling of solid-phase micro-extracting device:
A gas-chromatography is taken out with the stainless steel nook closing member that 5 μ L do not have the dead volume microsyringe, and with one section internal diameter 0.05-0.30mm with the same length of stainless steel nook closing member, the stainless steel capillary of external diameter 0.30-0.5mm is fixed in the injection device injector push rod, plug-in type fibre abstraction head is installed in the lower end of stainless steel capillary, forms simple and easy solid-phase micro-extracting device.
Advantage of the present invention and good effect:
1. be skillfully constructed, design is unique, by stainless steel capillary the extracting fiber head is connected with micro syringe, and is not only simple to operate, need not the complex interface device, and the making of fibre abstraction head and change all easy, quick, be applicable to the analysis several samples, simple and practical, cheap.
2. the good characteristic with the organic stephanoporate framework material of metal is applied to obtain Heat stability is good in the solid-phase micro-extracting device, and the extraction time is short, enrichment multiple height, and adsorption capacity is big, the solid-phase micro-extraction fibre that the range of linearity is wide.
3. on method, the organic stephanoporate framework material of metal is a big polyporous materials, nearly all can realize its growth at stainless steel surfaces by this method, thereby make this method have extensive applicability.From the sample analysis aspect, because this class material is mainly by the homogeneous duct, high specific area realizes extraction, so can come different compounds are carried out the high efficiency selective extraction by the organic stephanoporate framework material of the metal that makes up different ducts, this have broken the restriction of the conventional similar principle that mixes.The present invention is simple in structure, is easy to make, and has a extensive future.
[description of drawings]:
Fig. 1 is the fibre abstraction head that the surface has the organic stephanoporate framework material of metal;
Fig. 2 is the assembling simplified schematic diagram behind the fibre abstraction head insertion stainless steel capillary among Fig. 1;
Fig. 3 is the generalized section of extraction equipment.
Among the figure, 1 fibre abstraction head, 1-1 is the fibre abstraction head upper end after handling with chloroazotic acid, 1-2 is the fibre abstraction head lower end of the organic stephanoporate framework material of metal of having grown with HF processing and surface in situ, 2 stainless steel capillaries, 3 pull bar handles, 4 pull bars, 5 microsyringe outer tubes, 6 microsyringe syringe needles.
[specific embodiment]:
Below in conjunction with embodiment, novel solid phase micro extraction device of the present invention is described further, but the invention is not restricted to these embodiment.
The first, the preliminary treatment of metallic fiber:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the metallic fiber of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control metallic fiber external diameter is 0.05-0.20mm, an other end (about 1.5-4.0cm) of metallic fiber is placed HF, the room temperature corrosion was dried after the pure water rinsing to this section metallic fiber surface blackening in 20-40 minute.
The second, the metallic fiber surface in situ prepares the organic stephanoporate framework material of metal:
With 0.437g Cu
2(NO
3)
23H
20 is dissolved in the 6mL pure water, the 0.640g trimesic acid is dissolved in the 18mL absolute ethyl alcohol, mix behind the ultrasonic dissolution 10min respectively, mixed solution is placed 35mL polytetrafluoroethylene (PTFE) reactor, the metallic fiber that the first step makes is put into reactor, one end of HF corrosion immerses in the reaction mixture, 120 ℃ of reaction 8h.Question response still cooling, the metallic fiber of the organic stephanoporate framework material of metal that taken out superficial growth is removed surface solvent 120 ℃ of heating half an hour, can obtain having the solid phase micro-extracting head of the organic stephanoporate framework material of metal.See Fig. 1.
The first, the preliminary treatment of metallic fiber:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the metallic fiber of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control metallic fiber external diameter is 0.05-0.20mm, an other end (about 1.5-4.0cm) of metallic fiber is placed HF, the room temperature corrosion was dried after the pure water rinsing to this section metallic fiber surface blackening in 20-40 minute.
The second, the metallic fiber surface in situ prepares the organic stephanoporate framework material of metal:
With 0.580g Zn (NO
3)
26H
20, the 0.160g terephthalic acid (TPA) is dissolved in 20mL N, in the dinethylformamide, behind the ultrasonic dissolution 10min this solution is placed 35mL polytetrafluoroethylene (PTFE) reactor, the metallic fiber that the first step makes is put into reactor, one end of HF corrosion immerses in the reaction mixture, 120 ℃ of reaction 21h.Question response still cooling, the metallic fiber of the organic stephanoporate framework material of metal that taken out superficial growth is removed surface solvent 120 ℃ of heating half an hour, can obtain having the solid phase micro-extracting head of the organic stephanoporate framework material of metal.
Embodiment 3, surface are the preparation of the organic stephanoporate framework material of metal Zn (BDC) fibre abstraction head (dabco)
The first, the preliminary treatment of metallic fiber:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the metallic fiber of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control metallic fiber external diameter is 0.05-0.20mm, an other end (about 1.5-4.0cm) of metallic fiber is placed HF, the room temperature corrosion was dried after the pure water rinsing to this section metallic fiber surface blackening in 20-40 minute.
The second, the metallic fiber surface in situ prepares the organic stephanoporate framework material of metal:
With 0.50g Zn (NO
3)
26H
20,0.280g terephthalic acid (TPA), 0.094g the triethyl group diamines is dissolved in 20mL N, in the dinethylformamide, behind the ultrasonic dissolution 10min this solution placed 35mL polytetrafluoroethylene (PTFE) reactor, the metallic fiber that the first step makes is put into reactor, and an end of HF corrosion immerses in the reaction mixture, 120 ℃ of reaction 48h.Question response still cooling, the metallic fiber of the organic stephanoporate framework material of metal that taken out superficial growth is removed surface solvent 120 ℃ of heating half an hour, can obtain having the solid phase micro-extracting head of the organic stephanoporate framework material of metal.
Embodiment 4, surface are the preparation of the fibre abstraction head of the organic stephanoporate framework material of metal MIL-53 (Fe)
The first, the preliminary treatment of metallic fiber:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the metallic fiber of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control metallic fiber external diameter is 0.05-0.20mm, an other end (about 1.5-4.0cm) of metallic fiber is placed HF, the room temperature corrosion was dried after the pure water rinsing to this section metallic fiber surface blackening in 20-40 minute.
The second, the metallic fiber surface in situ prepares the organic stephanoporate framework material of metal:
The 0.4398g terephthalic acid (TPA) is dissolved in 20mL N, after dinethylformamide, ultrasonic 10min make its dissolving, to wherein adding 0.540g FeCl
36H
20, mixed solution is placed 35mL polytetrafluoroethylene (PTFE) reactor, the metallic fiber that the first step makes is put into reactor, and an end of HF corrosion immerses in the reaction mixture, 150 ℃ of reaction 48h.Question response still cooling, the metallic fiber of the organic stephanoporate framework material of metal that taken out superficial growth is removed surface solvent 150 ℃ of heating half an hour, can obtain having the solid phase micro-extracting head of the organic stephanoporate framework material of metal.
The first, the preliminary treatment of metallic fiber:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the metallic fiber of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control metallic fiber external diameter is 0.05-0.20mm, an other end (about 1.5-4.0cm) of metallic fiber is placed HF, the room temperature corrosion was dried after the pure water rinsing to this section metallic fiber surface blackening in 20-40 minute.
The second, the metallic fiber surface in situ prepares the organic stephanoporate framework material of metal:
The 0.072g terephthalic acid (TPA) is dissolved in the 20mL high purity water, after ultrasonic 10min makes its dissolving, to wherein adding 0.325gAl (NO
3)
39H
20, ultrasonic 10min places 35mL polytetrafluoroethylene (PTFE) reactor with mixed solution after making its dissolving, and the metallic fiber that the first step makes is put into reactor, and an end of HF corrosion immerses in the reaction mixture, 220 ℃ of reaction 72h.Question response still cooling, the metallic fiber of the organic stephanoporate framework material of metal that taken out superficial growth is removed surface solvent 220 ℃ of heating half an hour, can obtain having the solid phase micro-extracting head of the organic stephanoporate framework material of metal.
The first, the preliminary treatment of metallic fiber:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the metallic fiber of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control metallic fiber external diameter is 0.05-0.20mm, an other end (about 1.5-4.0cm) of metallic fiber is placed HF, the room temperature corrosion was dried after the pure water rinsing to this section metallic fiber surface blackening in 20-40 minute.
The second, the metallic fiber surface in situ prepares the organic stephanoporate framework material of metal:
With 0.325gCr (NO
3)
39H
20, HF solution (48wt%, 5mmol), 0.410g dioctyl phthalate is dissolved in the 20mL high purity water, ultrasonic 10min make its dissolving after, to wherein add ultrasonic 10min make its dissolving after, mixed solution is placed 35mL polytetrafluoroethylene (PTFE) reactor, the metallic fiber that the first step makes is put into reactor, and an end of HF corrosion immerses in the reaction mixture, 220 ℃ of reaction 8h.Question response still cooling, the metallic fiber of the organic stephanoporate framework material of metal that taken out superficial growth is removed surface solvent 220 ℃ of heating half an hour, can obtain having the solid phase micro-extracting head of the organic stephanoporate framework material of metal.
Embodiment 7, has the solid-phase micro-extracting device of the micro-extracting head of the organic stephanoporate framework material of metal
A gas-chromatography is taken out with the stainless steel nook closing member that 5 μ L do not have the dead volume microsyringe, the one section internal diameter 0.1mm with the same length of nook closing member that packs into, the stainless steel capillary 2 of external diameter 0.3mm, and this section stainless steel capillary is fixed on the microsyringe.The pull bar 4 of microsyringe is connected by pull bar handle 3 with stainless steel capillary 2, can be so that the push-and-pull in syringe of whole extracting fiber, usually the grown fibre abstraction head of the organic stephanoporate framework material of metal of surface in situ is hidden in the syringe needle, and the pull bar that can promote injector when needing makes fibre abstraction head 1 lean out in syringe needle 6 together with stainless steel capillary.
The grown end 1-1 of 0.09mm of fibre abstraction head 1 of the organic stephanoporate framework material of metal of the surface in situ that makes among the above embodiment is inserted in the stainless steel capillary 2, promptly finish the assembling of this device, see Fig. 3.
Claims (4)
1. solid-phase micro-extracting device, it is characterized in that this device comprises a microsyringe, stainless steel capillary as fiber bodies is installed in the injector push rod, the lower end of stainless steel capillary is equipped with plug-in type fibre abstraction head, the internal diameter of described stainless steel capillary is 50-300 μ m, external diameter is 200-500 μ m, described fibre abstraction head is that the organic stephanoporate framework material of metal of 30-200 μ m is formed by a stainless steel wire and by the thickness that growth in situ is coated in the stainless steel wire surface, and the preparation method of described fibre abstraction head is as follows:
The first, the preliminary treatment of stainless steel wire:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the stainless steel wire of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control stainless steel wire external diameter, making corrosion back stainless steel wire external diameter is 0.05-0.20mm, an other end of stainless steel wire is placed HF, and the room temperature corrosion was dried after the pure water rinsing to this section stainless steel wire surface blackening in 20-40 minute;
The second, the stainless steel wire surface in situ prepares the organic stephanoporate framework material of metal:
Put into water or ethanol or N in the hydrothermal reaction kettle, the dinethylformamide solvent, one or more slaines and one or more organic ligands be dissolved in the coordination ratio obtain reaction mixture in the solvent, the pretreated stainless steel wire of the first step is put into this hydrothermal reaction kettle, one end of HF corrosion immerses in the reaction mixture, the control reaction temperature is 50-220 ℃, and reaction time 6-90h makes the grown fibre abstraction head of the organic stephanoporate framework material of metal of surface in situ;
Described microsyringe is the no dead volume microsyringe of conventional gas-chromatography.
2. the preparation method of the fibre abstraction head in the described solid-phase micro-extracting device of claim 1 is characterized in that, comprises the steps:
The first, the preliminary treatment of stainless steel wire:
With an external diameter 0.05-0.3mm, the part of long 1.5-4.0cm places chloroazotic acid in the stainless steel wire of length overall 3.0-8.0cm, room temperature corrosion 20～60 minutes, by control etching time control stainless steel wire external diameter, making corrosion back stainless steel wire external diameter is 0.05-0.20mm, an other end of stainless steel wire is placed HF, and the room temperature corrosion was dried after the pure water rinsing to this section stainless steel wire surface blackening in 20-40 minute;
The second, the stainless steel wire surface in situ prepares the organic stephanoporate framework material of metal:
Put into water or ethanol or N in the hydrothermal reaction kettle, the dinethylformamide solvent, one or more slaines and one or more organic ligands be dissolved in the coordination ratio obtain reaction mixture in the solvent, the pretreated stainless steel wire of the first step is put into this hydrothermal reaction kettle, one end of HF corrosion immerses in the reaction mixture, the control reaction temperature is 50-220 ℃, and reaction time 6-90h makes the grown solid phase fibre abstraction head of the organic stephanoporate framework material of metal of surface in situ.
3. method according to claim 2 is characterized in that described slaine is inorganic metal salt copper nitrate, zinc nitrate, iron chloride, aluminum nitrate or chromic nitrate.
4. according to claim 2 or 3 described methods, it is characterized in that described organic ligand is terephthalic acid (TPA) or trimesic acid.
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| CN102019171B (en) * | 2010-08-12 | 2013-06-12 | 天津春发生物科技集团有限公司 | Belt-cyclodextrin matrix solid phase micro extraction coating and extraction head |
| CN102068963B (en) * | 2010-10-19 | 2013-07-10 | 天津春发生物科技集团有限公司 | Stainless steel solid phase micro extraction fiber |
| CN102091604A (en) * | 2010-12-22 | 2011-06-15 | 南开大学 | MOFs material-based series molecular sieve and preparation method and application method thereof in complex sample purification and separation analysis |
| CN102489105B (en) * | 2011-11-29 | 2014-02-26 | 南昌航空大学 | Air treatment device |
| CN102989432A (en) * | 2012-12-28 | 2013-03-27 | 南开大学 | Preparation of solid-phase microextraction (SPME) fiber and extraction device assembled by same |
| CN104226282A (en) * | 2013-06-20 | 2014-12-24 | 天津市汉沽合佳化工有限责任公司 | Adsorption material and extracting packet for micro solid phase extraction, and application method of extracting packet |
| CN104162291A (en) * | 2014-08-25 | 2014-11-26 | 武汉矽感科技有限公司 | Solid-phase micro-extraction device |
| CN105274596A (en) * | 2015-10-30 | 2016-01-27 | 西北师范大学 | Method for preparing nano-copper coating through electrodeposition |
| CN108579708B (en) * | 2018-04-28 | 2020-03-06 | 江南大学 | Solid-phase micro-extraction fiber for polycyclic aromatic hydrocarbon enrichment detection and manufacturing method thereof |
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| CN111974370B (en) * | 2020-06-23 | 2021-06-25 | 江南大学 | Electric field driven solid phase micro-extraction fiber and preparation method and application thereof |
| CN112945933A (en) * | 2021-02-05 | 2021-06-11 | 山东大学 | Method for rapidly detecting triphenylmethane chemicals in living biological tissues in situ |
| CN113607832B (en) * | 2021-06-30 | 2023-07-25 | 浙江工业大学 | Method for measuring fatty acid methyl ester in biodiesel wastewater by novel solid-phase microextraction technology |
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