CN103357391A - Ionic liquid sol-gel coating stirring rod, preparation method and applications - Google Patents

Ionic liquid sol-gel coating stirring rod, preparation method and applications Download PDF

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CN103357391A
CN103357391A CN2013103296722A CN201310329672A CN103357391A CN 103357391 A CN103357391 A CN 103357391A CN 2013103296722 A CN2013103296722 A CN 2013103296722A CN 201310329672 A CN201310329672 A CN 201310329672A CN 103357391 A CN103357391 A CN 103357391A
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ionic liquid
sol
gel coating
stirring rod
coating
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CN2013103296722A
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胡斌
范文莹
何蔓
陈贝贝
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武汉大学
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Abstract

The invention discloses an ionic liquid sol-gel coating stirring rod, a preparation method and applications, and belongs to the field of sample pre-treatment technology in analytical chemistry. The ionic liquid sol-gel coating stirring rod comprises a glass capillary, an iron core and an extraction coating. The iron core is arranged in the glass capillary and two ends of the glass capillary are fused and sealed. The extraction coating is 1-allylimidazole tetrafluoroborate ionic liquid gel coating which is chemically bonded on the surface of the glass capillary. The glass stirring rod activated by NaOH solution is soaked into ionic liquid sol to be coated, and then placed in a drying oven to be aged to obtain an ionic liquid sol-gel coating stirring rod. The ionic liquid sol-gel coating stirring rod can be used for extraction analysis of polar organic compounds. The ionic liquid sol-gel coating stirring rod has advantages of simple preparation, being environmentally friendly, high extraction efficiency, high-temperature resistance, organic solvent resistance, good mechanical stability and the like. The ionic liquid sol-gel coating stirring rod can realize selective extraction enrichment of organic compounds in sample systems of environment, food and biological samples and the like, and has practical application values.

Description

一种离子液体溶胶凝胶涂层搅拌棒及其制备方法与应用 An ionic liquid sol gel coating stir bar and preparation method and application

[0001] [0001]

技术领域 FIELD

[0002] 本发明属于分析化学样品前处理技术领域,涉及一种吸附型萃取搅拌棒,具体涉及一种离子液体溶胶凝胶涂层搅拌棒及其制备方法与应用。 [0002] The present invention belongs to the chemical sample prior to analysis processing technology, to a stir bar sorption extraction type, particularly relates to an ionic liquid sol-gel coating stir bar and a preparation method and application.

背景技术 Background technique

[0003]揽祥棒吸附萃取技术(SBSE)(Baltussen E., Sandra P., David F.,Cramers C.Stir bar sorptive extraction (SBSE), a novel extraction technique for aqueoussamples: theory and principles [J].Journal of Microcolumn Separations, 1999, [0003] Xiang embrace bar sorptive extraction (SBSE) (Baltussen E., Sandra P., David F., Cramers C.Stir bar sorptive extraction (SBSE), a novel extraction technique for aqueoussamples: theory and principles [J]. Journal of Microcolumn Separations, 1999,

11 (10): 737-747)作为一种新型的样品前处理技术,具有微型化、操作简便、成本低廉、萃取效率高等特点,与固相微萃取技术相比,避免了使用搅拌磁子造成的竞争吸附,较大的涂层体积增强了对目标分析物的萃取富集能力,具有更高的萃取效率,因而被广泛的应用于环境、食品及生物样品分析中。 11 (10): 737-747) was used as a sample before a new processing technology, with miniaturization, simple operation, low cost, and high extraction efficiency, as compared to solid-phase microextraction, it avoids the use of a magnetic stir caused by the competitive adsorption, the larger volume of the coating enhances the ability to accumulate the target analyte is extracted, has a higher extraction efficiency, they have been widely used in environmental, food, and biological sample analysis. 然而搅拌棒涂层的发展较为缓慢,目前应用较多的是针对苯系物、多环芳烃等非极性或弱极性化合物的非极性涂层聚二甲基硅氧烷(PDMS),因而制备适合不同极性且具有一定机械强度和化学稳定性的萃取涂层是目前SBSE的发展趋势之一。 However, the development is slow stirring bar coating, application of more current is directed to benzene, polycyclic aromatic hydrocarbons and other non-polar or non-polar coating weakly polar compound polydimethylsiloxane (PDMS), fiber coating thus prepared and having different polarities for certain mechanical strength and chemical stability is one of the current trends SBSE. [0004] 离子液体(ionic liquid)是一类由有机阳离子和无机/有机阴离子组成的、在接近室温条件下呈液态的盐类,具有较宽的液态温度范围、良好的溶解能力、较高的电导率和较宽的电化学窗口、较好的热稳定性和化学稳定性等优良性质,被形象地称为兼具液体和固体特性的“固态”液体(solid liquid)或“液体”分子筛(liquid zeolite)。 [0004] The ionic liquid (ionic liquid) is a class of organic cations and inorganic / organic anion, the salt is liquid at near room temperature, it has a wide liquid temperature range, good solvency, high excellent properties and a wider electrochemical window conductivity, good thermal stability and chemical stability, are referred to as the image characteristics of both solid and liquid "solid" liquid (solid liquid) or "liquid" molecular sieves ( liquid zeolite). 其中咪唑类离子液体因其对水和空气都稳定、成膜性能好、绿色安全等特性在合成化学、功能材料、生命科学和分离检测等领域都有广泛的应用(Maiti A.and Rogers RDAcorrelation-based predictor for pair-association in ionic liquids.PhysicalChemistry Chemical Physics.2011,13(26): 12138-12145; [3] Dupont J.,de SouzaR.F.,et al.1onic liquid (molten salt) phase organometallic catalysis.Chemical Reviews.2002,102(10): 3667-3691; [4] Blanchard LA,Hancu D.,Beckman EJ,et al.Green processing using ionic liquids and C02.Nature,1999,399(6731): 28-29)。 Wherein imidazolium ionic liquids are air and water because of its stability, good film-forming properties, green properties and the like have a wide safety in synthetic chemistry, functional materials, life science and other fields of detection and separation applications (Maiti A.and Rogers RDAcorrelation- based predictor for pair-association in ionic liquids.PhysicalChemistry Chemical Physics.2011,13 (26):. 12138-12145; [3] Dupont J., de SouzaR.F, et al.1onic liquid (molten salt) phase organometallic catalysis .Chemical Reviews.2002,102 (10): 3667-3691; [4] Blanchard LA, Hancu D., Beckman EJ, et al.Green processing using ionic liquids and C02.Nature, 1999,399 (6731): 28- 29). 在分离分析方面,离子液体已作为萃取相(Zhou X.,Xie PF,et al.Preparation and characterization of novel crown ether functionalizedionic liquid-based solid-phase microextraction coatings by sol-gel technology.Journal of Chromatography A.2011,1218(23): 3571-3580)、解吸剂(Martin-CaleroA.,Ayala JH, et al.1onic liquids as desorption solvents and memoryeffect suppressors in heterocyclic aromatic amines determination by SPME—HPLCfluorescence.Analytical and Bioanalytical Chemistry.2009, 394(4): 937-946)或中间介质等(Shearrow,AM,GAHarris, et al.1onic liquid-mediated sol-gelcoatings for capillary microextraction.Journal of Chromatography A.2009,1216(29): 5449-5458)用于改善萃取或解吸效率。 In the separation in the ionic liquid phase has (Zhou X., Xie PF, et al.Preparation and characterization of novel crown ether functionalizedionic liquid-based solid-phase microextraction coatings by sol-gel technology.Journal of Chromatography A.2011 as the extraction , 1218 (23): 3571-3580), the desorbent (Martin-CaleroA, Ayala JH, et al.1onic liquids as desorption solvents and memoryeffect suppressors in heterocyclic aromatic amines determination by SPME-HPLCfluorescence.Analytical and Bioanalytical Chemistry.2009, 394 (4): 937-946), or an intermediate medium or the like (Shearrow, AM, GAHarris, et al.1onic liquid-mediated sol-gelcoatings for capillary microextraction.Journal of Chromatography A.2009,1216 (29): 5449-5458) or for improving the extraction efficiency of desorption. 由于离子液体液态温度范围宽且溶解能力好,用物理涂覆方式制备的离子液体萃取涂层不耐浸入式萃取与溶剂解吸,多用于顶空萃取及热解吸,检出限较高且不能重复使用,有一定的局限性。 Ionic liquids wide range of temperatures and liquid good solubility, ionic liquids prepared by physically coating method a coating resistant to immersion extraction and extraction solvent desorption, used for extraction and headspace thermal desorption, a higher detection limit and can not re-use, there are some limitations.

发明内容 SUMMARY

[0005] 本发明的首要目的在于提供一种1-烯丙基咪唑四氟硼酸盐离子液体溶胶凝胶涂层搅拌棒,该搅拌棒适用于极性有机物的萃取分析,具有制备简单、环境友好、萃取效率高、耐高温、耐有机溶剂和机械稳定性好等优点。 [0005] The primary object of the present invention is to provide a 1-allyl-methylimidazolium tetrafluoroborate ionic liquid sol-gel coated stir bar was extracted stir bar applicable to the analysis of polar organics, and simple preparation, environmental Friendly, high extraction efficiency, high temperature resistance, good resistance to organic solvents and mechanical stability.

[0006] 本发明的另一目的在于提供上述离子液体溶胶凝胶涂层搅拌棒的制备方法,通过采用溶胶凝胶法,以KH-570 (Y-甲基丙烯酰氧基丙基三甲氧基硅烷)为桥联剂将含有双键基团的离子液体键合在玻璃搅拌棒表面,以避免在萃取和解吸过程中离子液体的流失。 [0006] Another object of the present invention is to provide the ionic liquid sol-gel coatings stirring rod prepared by sol-gel method, in KH-570 (Y- methacryloxypropyl trimethoxy silane) containing a crosslinking agent for the ionic liquid bond double bond group bonded loss in a glass stirring rod surface, to avoid the ionic liquid extraction and desorption process. 该方法解决了如何将对极性目标分析物具有较好萃取能力的离子液体引入搅拌棒涂层中,既保证有较高的萃取效率,又具有较好的热稳定性和化学稳定性,且机械稳定性好、可重复使用的技术问题。 The method addresses how the polarity of the target analyte will have better ionic liquid into the extraction ability stir bar coating, both to ensure a higher extraction efficiency, but also has good thermal and chemical stability, and good mechanical stability, re-use of technical problems.

[0007] 本发明的再一目的在于提供上述离子液体溶胶凝胶涂层搅拌棒的应用。 [0007] A further object of the present invention is to provide the ionic liquid sol-gel coating application stir bar.

[0008] 本发明的目的通过下述技术方案实现: [0008] The object of the present invention are achieved by the following technical scheme:

一种离子液体溶胶凝胶涂层搅拌棒,包括玻璃毛细管、铁芯和萃取涂层,铁芯置于两端熔封的玻璃毛细管内,萃取涂层涂覆在玻璃毛细管外表面;所述的萃取涂层为化学键合在玻璃毛细管表面的离子液体溶胶凝胶涂层;所述的离子液体优选为1-烯丙基咪唑四氟硼酸盐离子液体。 An ionic liquid sol gel coating stir bar, comprising a glass capillary, fiber coating and the core, the core was placed in a glass capillary tube sealed at both ends of melting and extracted coating is applied to the outer surface of the glass capillary; the extraction coating is chemically bonded sol-gel coating in an ionic liquid of the glass surface of the capillary; preferably the ionic liquid is 1-allyl-methylimidazolium tetrafluoroborate ionic liquid.

[0009] 所述的玻璃毛细管的尺寸优选为长2 cm、内径0.9-1.1 mm、壁厚0.10-0.15 mm,玻璃毛细管两端熔封形成哑铃型结构;所述的铁芯的尺寸优选为1.7 cm、直径0.50 mm。 [0009] The size of the glass capillary tube length is preferably 2 cm, an inner diameter of 0.9-1.1 mm, a wall thickness of 0.10-0.15 mm, a hermetically sealed glass capillary ends dumbbell-shaped structure is formed; the size of the core is preferably at least 1.7 cm, a diameter of 0.50 mm.

[0010] 上述离子液体溶胶凝胶涂层搅拌棒的制备方法,包括如下步骤: [0010] The method of preparing ionic liquid sol gel coating stir bar, comprising the steps of:

(I)玻璃搅拌棒的活化:将内设铁芯且两端熔封的玻璃毛细管置于NaOH溶液中进行活化,使玻璃毛细管外表面富含-OH基团,活化后清洗,烘干备用。 (I) activation of a glass stirring rod: and both ends of the iron core equipped with a hermetically sealed glass capillary was placed a solution of NaOH activated, the outer surface of the glass capillary rich -OH group, washing after activation, drying standby.

[0011] (2)离子液体溶胶的制备:将CH2Cl2 (二氯甲烷)、OH-PDMS (羟基封端聚二甲基硅氧烷)、TE0S (四乙氧基硅烷)、KH-570 ( Y -甲基丙烯酰氧基丙基三甲氧基硅烷)、[AIM] [BF4](1-烯丙基咪唑四氟硼酸盐)、PMHS (聚甲基氢硅氧烷)和TFA (三氟乙酸)混匀后,超声处理制得溶胶。 [0011] Preparation of ionic liquid sol (2): CH2Cl2 (dichloromethane), OH-PDMS (hydroxy-terminated polydimethylsiloxane), TE0S (tetraethoxysilane), KH-570 (Y - methacryloxypropyl trimethoxy silane), [AIM] [BF4] (1- allyl-tetrafluoroborate), PMHS (methyl hydrogen polysiloxane) and TFA (trifluoro after acetic acid) mixed, sonicated to obtain a sol.

[0012] (3)离子液体溶胶凝胶涂层搅拌棒的制备:将活化后的玻璃搅拌棒浸入离子液体溶胶中进行涂覆,取出后置于烘箱中老化,得到离子液体溶胶凝胶涂层搅拌棒。 [0012] Preparation of the rod (3) sol-gel coating liquid ionic stirring: a glass stirring rod activated after immersion ion sol liquid is coated, placed in an oven aging after extraction, to obtain an ionic liquid sol gel coating stir bar.

[0013] 步骤(I)中所述的氢氧化钠溶液的浓度优选为I mol/L。 [0013] Step (I) the concentration of the sodium hydroxide solution is preferably I mol / L.

[0014] 步骤(I)中所述的活化的时间优选为3 h以上。 [0014] Step (I) of the activation time is preferably 3 h.

[0015] 步骤(I)中所述的清洗优选为依次用超纯水、0.1 mol/L HCl (盐酸)、超纯水清洗至中性。 [0015] Step (I) is preferably in the washing sequentially with ultrapure water, 0.1 mol / L HCl (hydrochloric acid), ultrapure water until neutral.

[0016] 步骤(2)所述的离子液体溶胶的制备优选为:依次移取100 UL CH2Cl2 (二氯甲烷)、150 yL OH-PDMS (羟基封端聚二甲基硅氧烷)、100 μ L TEOS (四乙氧基硅烷)、60 μ LKH-570 ( Y-甲基丙烯酰氧基丙基三甲氧基硅烷)、30 uL [AIM] [BF4] (1-烯丙基咪唑四氟硼酸盐)、20 μ L PMHS (聚甲基氢娃氧烧)和40 μ L 95% (v/v) TFA (三氟乙酸),涡旋混匀后超声反应10 min制得溶胶。 [0016] Step (2) Preparation of the ionic liquid is preferably sol: sequentially pipetted 100 UL CH2Cl2 (dichloromethane), 150 yL OH-PDMS (hydroxy-terminated polydimethylsiloxane), 100 μ L TEOS (tetraethoxysilane), 60 μ LKH-570 (Y- methacryloxypropyl trimethoxy silane), 30 uL [AIM] [BF4] (1- allyl-imidazole tetrafluoroborate salt), 20 μ L PMHS (polymethyl hydrogen burning oxygen Wa) and 40 μ L 95% (v / v) TFA (trifluoroacetic acid), after vortexing ultrasonic sol prepared in 10 min.

[0017] 步骤(3)中所述的老化的条件优选为60°C老化3天。 [0017] The conditions of step (3) in the aging is preferably 60 ° C aging for 3 days.

[0018] 步骤(3)中在制备得到离子液体溶胶凝胶涂层搅拌棒后,优选再用甲醇超声清洗20 min。 [0018] Step (3) in the ionic liquid after the preparation of the sol-gel coating to obtain a stirring bar, preferably ultrasonic washing with methanol 20 min.

[0019] 制备离子液体溶胶的反应过程如图1所示。 [0019] The reaction process of preparing ionic liquid sol as shown in FIG.

[0020] 上述离子液体溶胶凝胶涂层搅拌棒在极性有机物的萃取分析中的应用。 Applications [0020] The ionic liquid sol gel coating with a stirring bar extraction in the analysis of polar organic.

[0021] 本发明具有如下优点与效果: [0021] The present invention has the following advantages and effects:

本发明将带有双键功能基的离子液体与KH-570化学键合,制备了一种萃取极性化合物且涂层性质稳定的离子液体溶胶凝胶涂层。 The present invention is a double bond with the ionic liquid functional group is chemically bonded with KH-570, a polar compound and the coating was extracted stable ionic liquid sol gel coating prepared. 利用溶胶凝胶法制备的离子液体溶胶凝胶涂层表面形貌较好,化学键合的方式增强了涂层的热稳定性和化学稳定性,适用于多种萃取和解吸模式。 Ionic liquid gel sol-gel prepared by a sol coating surface topography is preferably, chemically bonded manner enhances the thermal stability and chemical stability of the coating, for a variety of extraction and desorption mode. 涂层中的咪唑基团可与极性化合物产生疏水、氢键和作用等,能够实现在环境、食品以及生物样品等复杂样品体系中极性化合物的选择性萃取富集,有实际应用价值。 Coating imidazole group may generate polar compounds having a hydrophobic, hydrogen bonding and the like effect can be achieved in the selective enrichment of a complex sample extraction system environment, like foods and biological samples polar compounds, have practical value. 本发明的离子液体溶胶凝胶涂层搅拌棒适用于极性有机物的萃取分析,具有制备简单、环境友好、萃取效率高、耐高温、耐有机溶剂和机械稳定性好等优点。 Extraction rod suitable polar organic ionic liquid sol-gel coatings of the invention stirred analysis, simple preparation, environment-friendly, high extraction efficiency, high temperature, resistance to organic solvents and good mechanical stability.

附图说明 BRIEF DESCRIPTION

[0022] 图1是制备离子液体溶胶的反应过程图。 [0022] FIG. 1 is a sol prepared ionic liquid reaction process of FIG.

[0023] 图2是实施例1制备的离子液体溶胶凝胶涂层搅拌棒的结构示意图。 [0023] FIG. 2 is a schematic structural diagram of a sol-gel coating of an ionic liquid prepared in Example 1 embodiment stir bar.

[0024] 图3是实施例1制备的离子液体溶胶凝胶涂层的红外光谱图,(a)为不含离子液体的溶胶凝胶涂层,(b)为含离子液体的溶胶凝胶涂层。 [0024] FIG. 3 is an infrared spectrum of the ionic liquid sol gel coating prepared according to Example 1, (a) a sol-gel coating is free of an ionic liquid, (b) containing an ionic liquid sol-gel coating Floor.

[0025] 图4是实施例1制备的离子液体溶胶凝胶涂层搅拌棒用扫描电镜表征的表面形貌图。 [0025] FIG. 4 is a rod with a surface topography characterized by scanning electron microscopy ionic liquid sol gel coating prepared in Example 1 was stirred.

[0026] 图5是实施例1制备的离子液体溶胶凝胶涂层的热重表征图。 [0026] FIG. 5 is a view of a plasma characterized by Thermogravimetric sol-gel coating liquid prepared in Example 1.

[0027] 图6是实施例1制备的离子液体溶胶凝胶涂层的耐酸碱、耐有机溶剂性能考察图。 [0027] FIG. 6 is an acid ionic liquid sol gel coating prepared according to Example 1, resistance to organic solvents High Performance FIG.

[0028] 图7是实施例1制备的离子液体溶胶凝胶涂层搅拌棒的使用寿命考察图。 [0028] FIG. 7 is an ionic liquid lifetime investigation sol gel coating prepared in Example 1 embodiment stir bar.

[0029] 图8是实施例1制备的离子液体溶胶凝胶涂层搅拌棒应用于SBSE-HPLC-UV检测环境样品中三种非留体类抗炎药(酮洛芬,萘普生,芬布芬)的色谱图;A、B、C、D分别为东湖水样、未名湖水样、尿样、牛奶样品;(a)为样品不经过搅拌棒吸附萃取,直接进入高效液相色谱-紫外的色谱图;(b)为样品经过搅拌棒吸附萃取解吸步骤,其解吸液进入高效液相色谱-紫外的色谱图;(c)为先在样品中预先加入待测目标分析物(酮洛芬、萘普生和芬布芬)的标准液(100 ppb),然后再经过搅拌棒吸附萃取过程,将解吸液进入高效液相色谱-紫外的色谱图。 [0029] FIG. 8 is a stir bar SBSE-HPLC-UV is applied to environmental samples Three non-steroidal anti-inflammatory drug (ketoprofen, naproxen ionic liquid sol gel coating prepared according to Example 1, Finland Bufen) chromatogram; a, B, C, D are Lake water samples, water samples Weiminghu, urine, milk samples; (a) sample without stir bar sorptive extraction, directly into the liquid chromatograph - ultraviolet chromatograms; (b) a sample stir bar sorptive extraction through the desorption step of desorbing fluid into the high performance liquid chromatography - ultraviolet chromatograms; (c) for the first sample in advance a target analyte to be added (ketorolac Fen, naproxen and fenbufen) standard solution (100 ppb), and then stir bar sorptive extraction process after the desorption solution into the liquid chromatograph - UV chromatogram of FIG.

具体实施方式 Detailed ways

[0030] 下面结合实施例及附图对本发明做进一步详细的描述,但本发明的实施方式不限于此。 [0030] below with reference to accompanying drawings, and the present invention is described in further detail in the Examples, but the embodiment of the present invention is not limited thereto.

[0031] 一种离子液体溶胶凝胶涂层搅拌棒,如图2所示,包括玻璃毛细管2、铁芯I和萃取涂层3,铁芯I置于两端熔封的玻璃毛细管2内,萃取涂层3涂覆在玻璃毛细管外表面。 [0031] A sol-gel coating liquid ionic stirring bar, shown in Figure 2, comprises a glass capillary 2, the core I and the fiber coating 3, I core 2 disposed within glass capillary tube sealed at both ends of the melting, extracted 3 coating the outer surface of the coated glass capillary. 萃取涂层为化学键合在玻璃毛细管表面的离子液体溶胶凝胶涂层,离子液体为1-烯丙基咪唑四氟硼酸盐离子液体。 Extraction coating is chemically bonded to the glass surface of the capillary of the sol-gel coating an ionic liquid, the ionic liquid is 1-allyl-methylimidazolium tetrafluoroborate ionic liquid.

[0032] 实施例1 [0032] Example 1

(I)制备哑铃型玻璃搅拌棒 (I) Preparation of a dumbbell-shaped glass stir rod

将直径为0.50 mm的细铁丝截成长为1.7 cm的小段,用砂纸打磨光滑笔直,再将内径 Then the inner diameter of the thin wire having a diameter of 0.50 mm was cut to grow 1.7 cm pieces, sanded smooth and straight,

0.9-1.1 _、壁厚0.10-0.15 mm的玻璃毛细管(购于华西医科大学仪器厂)截成长度约为2.5 cm的小段。 _ 0.9 to 1.1, the wall thickness of 0.10-0.15 mm glass capillaries (available from West China University of Medical Instrument Factory) cut to a length of the small pieces of about 2.5 cm. 将处理过的细铁丝置于玻璃毛细管中,毛细管两端用酒精灯火焰熔封并形成隆起,最终得到长度为2 cm的哑铃型玻璃搅拌棒。 The treated thin wire placed in a glass capillary, the capillary ends capped with an alcohol lamp flame spraying and forms a ridge, a length of 2 cm finally obtained dumbbell glass stirring rod.

[0033] (2)玻璃搅拌棒的活化 [0033] (2) activation of a glass stirring rod

将制备好的哑铃型搅拌棒依次用超纯水和甲醇清洗,再置于I mol/L NaOH中活化3 h以上,活化完后取出,再依次用超纯水、0.1 mol/L HC1、超纯水清洗至中性,置于烘箱中烘干备用。 The dumbbell-shaped stir bar prepared with ultrapure water, and sequentially washed with methanol, then placed I mol / L NaOH activation than 3 h, taken out after the activation, then washed with ultra-pure water, 0.1 mol / L HC1, super pure water until neutral, dried in an oven use.

[0034] (3)离子液体溶胶的制备 Preparation of [0034] (3) ionic liquid sol

依次移取100 UL CH2Cl2 (二氯甲烷)、150 μ L OH-PDMS (羟基封端聚二甲基硅氧烷,Μ.ff.4200),100 μ L TEOS (四乙氧基硅烷)、60 μ L ΚΗ-570 ( Y -甲基丙烯酰氧基丙基三甲氧基硅烷)、30 UL [AIM] [BF4] (1_烯丙基咪唑四氟硼酸盐)(购于上海成捷化学有限公司(上海,中国))、20 uL PMHS (聚甲基氢硅氧烷)和40 μ L 95% (ν/ν)的TFA,涡旋混匀后超声反应10 min制得溶胶。 Sequentially pipetted 100 UL CH2Cl2 (dichloromethane), 150 μ L OH-PDMS (hydroxy-terminated polydimethylsiloxane, Μ.ff.4200), 100 μ L TEOS (tetraethoxysilane), 60 μ L ΚΗ-570 (Y - methacryloxypropyl trimethoxy silane), 30 UL [AIM] [BF4] (1_ allyl tetrafluoroborate) (purchased from Shanghai chemical Jie into Co., Ltd. (Shanghai, China)), after 20 uL PMHS (methyl hydrogen polysiloxane) and 40 μ L 95% (ν / ν) of TFA, in 10 min vortexing ultrasonic prepared sol.

[0035] (4)离子液体溶胶凝胶涂层搅拌棒的制备 [0035] (4) sol-gel coatings prepared ionic liquid stirring rod

将活化后的玻璃搅拌棒浸入离子液体溶胶中进行涂覆,取出置于烘箱中60 °C老化3天,得到离子液体溶胶凝胶涂层搅拌棒。 The activated glass stirring rod immersed in the ionic liquid sol coating removed in an oven aging 60 ° C for 3 days to give the ionic liquid a sol-gel coating stir bar. 所制备的离子液体溶胶凝胶涂层搅拌棒在使用前需先用甲醇超声清洗20 min,以除去搅拌棒表面的有机物杂质。 Ionic liquid sol gel coating prepared before use stir bar at 20 min before washing with methanol ultrasound, in order to remove organic impurities stir bar surface.

[0036] 对制备得到的离子液体溶胶凝胶涂层搅拌棒进行红外检测、扫描电镜分析和热重分析,结果如下: [0036] The ionic liquid was stirred sol gel coating prepared infrared detection rod, electrical analysis and thermogravimetric analysis of the scanning, the following results:

图3是离子液体溶胶凝胶涂层的红外光谱图,图中比较了(a)不加离子液体的溶胶凝胶涂层与(b)加离子液体的溶胶凝胶涂层的红外峰。 FIG 3 is an infrared spectrum of the ionic liquid sol-gel coating, sol-gel coating of the IR peaks of FIG comparing (a) the ionic liquid without the sol-gel coating and (b) adding an ionic liquid. 从图中可以看出,2970 CnT1为碳碳双键(C=C)的特征吸收峰,加了离子液体反应后双键峰几乎消失,2360 cm—1为离子液体硼氟键(BF)键的特征吸收峰,666 CnT1为离子液体咪唑环的特征吸收峰,由此可以认为离子液体 As can be seen from the figure, 2970 CnT1 carbon-carbon double bonds (C = C) characteristic absorption peaks, the reaction liquid after the addition of ionic double peak almost disappeared, 2360 cm-1 is a boron-fluorine bonds ionic liquid (BF) key characteristic absorption peaks, 666 CnT1 absorption of the imidazole ring wherein the ionic liquid, the ionic liquid can thus be considered

1-烯丙基咪唑四氟硼酸盐确实通过双键键合的方式参与溶胶凝胶反应。 1-allyl-imidazole tetrafluoroborate indeed involved in sol-gel reaction by way of a double bond.

[0037] 图4是离子液体溶胶凝胶涂层搅拌棒用扫描电镜表征的表面形貌图。 [0037] FIG. 4 is a rod with a surface topography characterized by scanning electron microscopy ionic liquid sol gel coating stirred. 离子液体参与溶胶凝胶反应,不仅可以作为萃取材料对目标分析物有很好的萃取富集,同时还具有分子自组装的作用改善溶胶凝胶涂层的表面形貌。 Ionic liquids involved in sol-gel reaction, not only as a target analyte extracted material have a good extraction enrichment, but also self-assembling molecules having the effect of improving the surface morphology of the sol-gel coating. 从扫描电镜图可以看出制备的离子液体涂层搅拌棒表面光滑均匀,成膜性较好,涂层表面可以看到均一的膜孔结构,孔径约为3-5μ m0 From the SEM can be seen the preparation of ionic liquids stirring bar coating uniformly smooth surface, good film forming properties, the coating film surface can be seen that a uniform pore structure, pore size of about 3-5μ m0

[0038] 图5是离子液体溶胶凝胶涂层的热重表征图。 [0038] FIG. 5 is a thermionic liquid sol-gel coating weight characterization FIG. 从热重分析图中可以看到,离子液体涂层在200°C之前有轻微质量变化,这主要是由涂层中未参与溶胶凝胶反应的反应原料分解造成的,在360°C之前萃取功能涂层性质稳定,之后温度升高涂层有明显失重,失重区间为360-609°C,在这段过程中质量下降主要是由萃取溶胶凝胶涂层的分解造成的,材料发生了不可逆变化。 Thermal analysis can be seen from the figure, the ionic liquid coating quality vary slightly before 200 ° C, the reaction mainly by the coating material are not involved in sol-gel reaction caused by the decomposition of 360 ° C prior to extraction stable functional coating, the coating after significant weight loss temperature is raised, weight loss interval 360-609 ° C, during which process quality degradation is mainly caused by the decomposition of extracted sol-gel coating material occurs irreversibly Variety. 由此可见,所制备的材料可以承受360°C以内的温度变化,热稳定性较好,适用于热解吸操作。 Thus, the material produced can withstand a temperature change within 360 ° C, good thermal stability, suitable for thermal desorption operation.

[0039] 实施例2 [0039] Example 2

离子液体溶胶凝胶涂层搅拌棒的萃取解吸过程如下:将离子液体溶胶凝胶涂层搅拌棒置于10 mL样品溶液中,在800 rpm转速下搅拌萃取30 min,萃取结束后取出搅拌棒,用滤纸擦干搅拌棒表面的溶液残留,将其转移至装有100 μ L甲醇的解吸管中超声解吸15 min。 Ionic liquid sol gel coating stir bar was extracted desorption process is as follows: ionic liquid sol gel coatings stirring bar was placed in a 10 mL sample solution, stirred at 800 rpm speed was extracted 30 min, remove the stir bar after extraction, the solution was stirred with a rod surface residual dry filter paper, transferred to a desorption tube containing 100 μ L of methanol desorption ultrasound 15 min. 解吸液经0.22 μ m滤膜过滤后用于后续高效液相色谱-紫外(HPLC-UV)检测分析;解吸后的搅拌棒置于甲醇中超声5 min,再生后可重复使用。 After desorption solution 0.22 μ m filter membrane for subsequent HPLC - UV detection and analysis (HPLC-UV); desorbed stirring rod is placed in an ultrasonic methanol 5 min, may be reused after regeneration.

[0040] 由于离子液体溶胶凝胶涂层搅拌棒为直接浸入式萃取,且用有机溶剂解吸,因而对所制备的离子液体萃取涂层进行了耐酸碱、耐有机溶剂性能的考察。 [0040] Since the ionic liquid sol-gel coating stir bar direct immersion extraction with an organic solvent and desorption, and thus the ionic liquid extraction were prepared by coating acid, an organic solvent-resistant properties investigated. 将实施例1制备得到的离子液体溶胶凝胶涂层搅拌棒分别浸没于I mol/L HC1、0.1 mol/L HClU mol/LNa0H、0.1 mol/L NaOH、甲醇和乙腈里,24 h后取出,超纯水清洗;按照上述方法将处理过离子液体溶胶凝胶涂层搅拌棒的分别置于含400 μ g/L酮洛芬(KEP)、萘普生(NAP)、芬布芬(FBF)的样品溶液中进行萃取解吸,比较其萃取效率变化,结果如图6所示,可以看出制备的离子液体涂层搅拌棒耐受碱和有机溶剂的能力相当,耐受酸的能力稍弱,具有较好的化学稳定性。 Stir bar sol gel coating prepared ionic liquid obtained in Example 1 were immersed in the embodiment I mol / L HC1,0.1 mol / L HClU mol / LNa0H, 0.1 mol / L NaOH, methanol and acetonitrile in 24 h later removed ultrapure water; as described above the treated ionic liquid sol-gel coating containing a stir bar were placed 400 μ g / L ketoprofen (KEP), naproxen (NAP), fenbufen (FBF) the sample solution was extracted desorption, comparing the extraction efficiency change, results shown in Figure 6, it can be seen that the ability to withstand the rod base and organic solvent prepared by coating an ionic liquid considerable agitation, the ability to tolerate weaker acid, It has good chemical stability.

[0041] 按照上述离子液体溶胶凝胶涂层搅拌棒的萃取解吸的方法,将实施例1制备得到的离子液体溶胶凝胶涂层搅拌棒重复使用50次,通过对酮洛芬(KEP)、萘普生(NAP)、芬布芬(FBF)的萃取效率考察其使用寿命。 The method of extraction desorption [0041] stirring rod according to the ionic liquid sol-gel coating, the sol-gel coating embodiment the ionic liquid prepared in Example 1 was repeated using the stir bar 50 times by ketoprofen (KEP), naproxen (NAP), fenbufen (FBF) extraction efficiency study of its useful life. 结果如图7所示,从图中可以看出,离子液体溶胶凝胶涂层搅拌棒萃取解吸50次后对酮洛芬(KEP)、萘普生(NAP)、芬布芬(FBF)的萃取效率无明显变化,且重复使用过程中搅拌棒涂层无磨损脱落现象,可见离子液体涂层具有较好的机械性能及稳定的萃取效果,可使用至少50次。 The results shown in Figure 7, can be seen from the figure, the ionic liquid extracted sol-gel coating stir bar 50 after desorption of ketoprofen (KEP), naproxen (the NAP), fenbufen (FBF) of no significant change of extraction efficiency, and repeated use stirring bar coating wear off phenomenon, visible ionic liquid coating having good mechanical properties and stability of the extraction efficiency can be used at least 50 times.

[0042] 实施例3 [0042] Example 3

将实施例1制备的离子液体溶胶凝胶涂层搅拌棒应用于搅拌棒吸附萃取-高效液相色谱-紫外检测(SBSE-HPLC-UV)分析复杂样品中的三种非留体类抗炎药(酮洛芬、萘普生和芬布芬),经过一系列条件优化得到最佳的萃取解吸和分离检测条件。 High Performance Liquid Chromatography - - stir bar sorptive extraction rod applied sol-gel coating an ionic liquid prepared in Example 1 was stirred with UV detection (SBSE-HPLC-UV) analysis of three kinds of non-steroidal anti-inflammatory drugs in complex samples (ketoprofen, naproxen and fenbufen), through a series of extraction conditions are optimized to give the best separation desorption and detection conditions. 最佳的萃取解吸条件为:样品溶液PH为3,NaCl的质量浓度为15%,萃取温度为20°C,搅拌速率为800 rpm,萃取时间为30 min ;解吸剂为体积比为7:3的甲醇:10 mM NaOH溶液,超声解吸15 min。 Desorption conditions for optimum extraction: the sample solution as PH 3, and NaCl was 15%, the extraction temperature is 20 ° C, a stirring rate of 800 rpm, the extraction time was 30 min; desorbent to volume ratio of 7: 3 methanol: 10 mM NaOH solution, sonicated desorption 15 min. 最佳的HPLC-UV分离检测条件为:Agilent 1100高效液相色谱(Agilent Technologies,ffaldbronn, Germany),配置有在线脱气机、四元混合泵、100 μ L定量环、可变波长紫外检测器,色谱柱为RP_18 柱(4.6 mmX 250 mm,粒径5 μ m, Merck KgaA, Germany);以甲醇:10 mmol/L磷酸缓冲溶液(体积比为63:37,pH 3)为色谱流动相,室温等度洗脱,流速I mL/min ;紫外检测波长210 nm ;进样体积30 μ L。 Separating the best HPLC-UV Detection conditions: Agilent 1100 HPLC (Agilent Technologies, ffaldbronn, Germany), arranged online degasser, quaternary mixing pump, 100 μ L sample loop, a variable wavelength UV detector column was RP_18 column (4.6 mmX 250 mm, particle size 5 μ m, Merck KgaA, Germany); methanol: 10 mmol / L phosphate buffer solution (volume ratio of 63: 37, pH 3) as the chromatographic mobile phase, rt isocratic, flow rate I mL / min; UV detection wavelength 210 nm; injection volume was 30 μ L. 然后在最佳实验条件下分析环境、生物和食品样品中目标分析物,具体选择的样品及预处理过程如下: Then analysis of environmental, biological and food samples target analyte under optimal conditions, the particular choice of sample and pretreatment process is as follows:

(I)环境水样:东湖水和校园湖水分别是在东湖(武汉,中国)和武汉大学未名湖(武汉,中国)采集的表层水。 (I) in environmental water samples: East Lake and East Lake campus in the lake are (Wuhan, China) and Wuhan University Weiming Lake (Wuhan, China) collected surface water. 水样经0.45 μπι滤膜过滤,并用NaCl调节盐浓度为质量浓度15%、Imol/L HCl 调节pH 为3.0。 0.45 μπι water samples by membrane filtration, and the salt concentration adjusted with NaCl concentration of 15%, Imol / L HCl adjusted to pH 3.0.

[0043] (2)尿样:尿样由实验室健康人提供,检测前需要先用0.45 ym滤膜过滤,然后用超纯水按1:1比例稀释,同时调节盐浓度为15%、pH为3.0。 [0043] (2) urine: urine laboratory by healthy people, with the need to pre-test 0.45 ym filter membrane, with ultrapure water and then press 1: 1 dilution ratio, while adjusting the salt concentration of 15%, pH 3.0.

[0044] (3)牛奶样品:新鲜纯牛奶购于本地超市(武汉,中国)。 [0044] (3) a sample of milk: fresh milk purchased from a local supermarket (Wuhan, China). 准备移取4.0 mL牛奶于50 mL定量管中,加入目标分析物NSAIDs标液,涡旋2 min混匀,用超纯水稀释,调节NaCl为15%、pH为3.0,定容至40 mL刻度。 Pipette 4.0 mL prepared in 50 mL quantitative milk tube, add NSAIDs target analyte standard solution, mix vortexed 2 min, diluted with ultrapure water, adjusting the NaCl was 15%, pH of 3.0 and dilute to 40 mL scale . 超声提取30 min后用0.45 μπι滤膜过滤以分离蛋 After the ultrasonic extraction with 30 min 0.45 μπι membrane filter to separate the egg

白和脂肪等复杂基质。 Complex matrix and white fat.

[0045] 搅拌棒吸附萃取-高效液相色谱-紫外检测(SBSE-HPLC-UV)分析环境样品中三种非留体类抗炎药(酮洛芬、萘普生和芬布芬)的色谱图如图8所示:Α、B、C、D分别为东湖水样、未名湖水样、尿样、牛奶样品;图中(a)为样品不经过搅拌棒吸附萃取,直接进入高效液相色谱-紫外的色谱图;图中(b)为样品经过搅拌棒吸附萃取解吸步骤,其解吸液进入高效液相色谱-紫外的色谱图;图中(c)为先在样品中预先加入待测目标分析物(酮洛芬、萘普生和芬布芬)的标准液(100 μ g/L),然后再经过搅拌棒吸附萃取过程,将解吸液进入高效液相色谱-紫外的色谱图。 [0045] Stir Bar Sorptive Extraction - HPLC - UV (SBSE-HPLC-UV) analysis of environmental samples three kinds of non-steroidal anti-inflammatory drug (ketoprofen, naproxen and fenbufen) chromatography Α, B, C, D East Lake water samples, water samples Weiminghu, urine, milk samples, respectively; FIG. (a) without stir bar sorptive extraction sample directly into the liquid: as shown in FIG. FIG. 8 chromatography - UV chromatograms; figure (b) in the sample after the desorption step stir bar sorptive extraction, desorption solution into the liquid chromatograph - UV chromatogram; and FIG. (c) is added to the sample to be tested in advance target analyte standard solution (ketoprofen, naproxen and fenbufen) of (100 μ g / L), then through the stir bar sorptive extraction process, the desorption solution into the liquid chromatograph - UV chromatogram of FIG. 从对比图可知;四种样品中均未检测到三种目标分析物,且本方法对基体相对复杂的尿样和牛奶样品有较好的抗基体干扰能力,可以实现萃取富集目标分析(酮洛芬、萘普生和芬布芬)的目的,有很好的应用价值。 It is seen from the comparison chart; four samples was not detected in three kinds of target analyte, and the present method has good resistance to substrate interference relatively complex matrix of urine and milk samples, analysis Enrichment - target (one can be achieved ketoprofen, naproxen and fenbufen) purposes, a very good value.

[0046] 上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。 [0046] The preferred embodiment of the present invention embodiment, but the embodiment of the present invention is not limited to the above embodiments, changes made to any other without departing from the spirit and principle of the present invention, modifications, substitutions , combined, simplified, should be equivalent replacement method, it is included within the scope of the present invention.

Claims (10)

1.一种离子液体溶胶凝胶涂层搅拌棒,其特征在于:包括玻璃毛细管、铁芯和萃取涂层,铁芯置于两端熔封的玻璃毛细管内,萃取涂层涂覆在玻璃毛细管外表面;所述的萃取涂层为化学键合在玻璃毛细管表面的离子液体溶胶凝胶涂层。 An ionic liquid sol-gel coating stir bar, characterized by: a glass capillary, fiber coating and the core, the core was placed in a glass capillary tube sealed at both ends of melting and extracted coating is applied to the glass capillary an outer surface; said coating is extracted chemically bonded sol-gel coating in an ionic liquid of the glass surface of the capillary.
2.根据权利要求1所述的离子液体溶胶凝胶涂层搅拌棒,其特征在于:所述的离子液体为1-烯丙基咪唑四氟硼酸盐离子液体。 2. The ionic liquid of the sol-gel coating according to claim 1, a stirring rod, wherein: said ionic liquid is 1-allyl-methylimidazolium tetrafluoroborate ionic liquid.
3.根据权利要求1所述的离子液体溶胶凝胶涂层搅拌棒,其特征在于:所述的玻璃毛细管的尺寸为长2 cm、内径0.9-1.1 _、壁厚0.10-0.15 _,玻璃毛细管两端熔封形成哑铃型结构;所述的铁芯的尺寸为1.7 cm、直径0.50 mm。 The ionic liquid of the sol-gel coating as claimed in claim 1, a stirring rod, wherein: the size of the glass capillary is 2 cm long, internal diameter 0.9-1.1 _, _ 0.10-0.15 wall thickness, the glass capillary dumbbell-shaped ends forming a hermetically sealed structure; the size of the core of 1.7 cm, a diameter of 0.50 mm.
4.权利要求1-3任一项所述的离子液体溶胶凝胶涂层搅拌棒的制备方法,其特征在于包括如下步骤:(1)玻璃搅拌棒的活化:将内设铁芯且两端熔封的玻璃毛细管置于NaOH溶液中进行活化,活化后清洗,烘干备用;(2)离子液体溶胶的制备:将二氯甲烷、羟基封端聚二甲基硅氧烷、四乙氧基硅烷、Y-甲基丙烯酰氧基丙基三甲氧基硅烷、1-烯丙基咪唑四氟硼酸盐、聚甲基氢硅氧烷和三氟乙酸混匀后,超声处理制得溶胶;`(3)离子液体溶胶凝胶涂层搅拌棒的制备:将活化后的玻璃搅拌棒浸入离子液体溶胶中进行涂覆,取出后置于烘箱中老化,得到离子液体溶胶凝胶涂层搅拌棒。 Ionic liquid sol gel coating according to any of claims 1 to 3 bar stirring preparation, characterized by comprising the steps of: (1) activation of a glass stirring rod: and both ends of the core features placed in a hermetically sealed glass capillary NaOH solution was activated after activation cleaning, drying standby; preparation of ionic liquid sol (2): dichloromethane, hydroxy-terminated polydimethylsiloxane, tetraethoxy silane, Y- methacryloxypropyl trimethoxy silane, the 1-allyl-methylimidazolium tetrafluoroborate, methyl hydrogen polysiloxane trifluoroacetic acid and mixing, sonication to obtain a sol; `(3) preparation of ionic liquid sol-gel stick coating stirring: the activated glass stirring rod immersion ion sol liquid is coated, placed in an oven aging after extraction, to obtain an ionic liquid sol gel coating stir bar .
5.根据权利要求4所述的离子液体溶胶凝胶涂层搅拌棒的制备方法,其特征在于:步骤(I)中所述的氢氧化钠溶液的浓度为I mol/L ;所述的活化的时间为3 h以上。 Said activation; concentration step (I) in the sodium hydroxide solution is I mol / L: 5. The ionic liquid sol-gel coating as claimed in claim 4, wherein the stirring rod prepared, wherein the time is more than 3 h.
6.根据权利要求4所述的离子液体溶胶凝胶涂层搅拌棒的制备方法,其特征在于:步骤(I)中所述的清洗为依次用超纯水、0.1 mol/L HC1、超纯水清洗至中性。 The ionic liquid sol-gel coating as claimed in claim 4, wherein the stirring rod production method, wherein: the washing step (I) is in the ultrapure water successively, 0.1 mol / L HC1, ultrapure washed with water until neutral.
7.根据权利要求4所述的离子液体溶胶凝胶涂层搅拌棒的制备方法,其特征在于:步骤(2)所述的离子液体溶胶的制备为:依次移取100 yL 二氯甲烷、150 yL羟基聚封端~■甲基娃氧烧、100 μ L四乙氧基娃烧、60 u LY _甲基丙稀酸氧基丙基二甲氧基娃烧、30μ L 1-烯丙基咪唑四氟硼酸盐、20 UL聚甲基氢娃氧烧和40 μ L三氟乙酸,涡旋混匀后超声反应10 min制得溶胶。 The ionic liquid sol-gel coating as claimed in claim 4, wherein the stirring rod production method, wherein: the step (2) Preparation of the ionic liquid sol: dichloromethane sequentially pipetted 100 yL, 150 yL ~ ■ hydroxy-terminated poly methyl baby oxygen burning, 100 μ L baby burn tetraethoxysilane, 60 u LY _ propyl dimethoxy methyl acrylic baby burn, 30μ L 1- allyl tetrafluoroborate, 20 UL baby polymethyl hydrogen and oxygen to burn 40 μ L of trifluoroacetic acid. after vortexing ultrasonic sol prepared in 10 min.
8.根据权利要求4所述的离子液体溶胶凝胶涂层搅拌棒的制备方法,其特征在于:步骤(3)中所述的老化的条件为60°C老化3天。 Ionic liquid according to claim 4, wherein the sol-gel coating method for preparing stirring rod, wherein: the step (3) the aging conditions of 60 ° C aging for 3 days.
9.根据权利要求4所述的离子液体溶胶凝胶涂层搅拌棒的制备方法,其特征在于:步骤(3)中在制备得到离子液体溶胶凝胶涂层搅拌棒后,再用甲醇超声清洗20 min。 Ionic liquid according to claim 4, wherein the sol-gel coating method for preparing stirring rod, wherein: the step (3) in the ionic liquid after the preparation of the sol-gel coating to obtain a stirring bar, ultrasonic cleaning with methanol 20 min.
10.权利要求1-3任一项所述的离子液体溶胶凝胶涂层搅拌棒在极性有机物的萃取分析中的应用。 10. The ionic liquid sol gel coating according to any of claims 1 to 3 bar in the application of extracted polar organic analysis stirred.
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