| Since its introduction in 1914,ionic liquids(ILs)have provided a new way to solve the problems of environmental pollution.Compared with traditional organic solvents,ILs have many unique advantages.First,negligible vapor pressure and low flammability make ILs safe and environmental friendly in both usage and storage.Second,ILs can remain liquid in a wide temperature range.Some ILs can even keep liquid when the temperature is far below room temperature or up to 300?.Third,ILs can be designed by changing the cations or the anions,so there are more than one trillion kinds of ILs in theory.Fourth,ILs have good solubility,which can dissolve many organic,inorganic and polymer materials,thus making it be used as the extraction solvent or the catalyst carrier.Fifth,ILs have good biocompatibility,which is expected to serve as active drug carriers and promote the clinical promotion of drugs.According to the research,composite materials which combine the advantages of ILs with other materials can make the use of ILs and meet more requirements.Functionalized composites will lead a new trend in the future.Solid-phase extraction(SPE)is a kind of sample pretreatment technology which has been developed in recent years.Based on the principle of selective adsorption and elution,SPE can separate analytes in complex matrix.SPE is a simple,solvent free method that combines enrichment and purification into one step.SPE is also easy to be connected with modern analytical instruments in order to realize automation.Therefore,SPE has developed quickly in environment,clinical analysis and other areas.However,domestic commercial SPE method mainly depends on imported extraction column at present.Thus,it is urgent to improve the stability of extraction coatings,guarantee the extraction recovery,develop new extraction coatings and expand its application.Applying the new analysis methods and new strategies developed in the laboratory to the actual production and life is the final purpose of analytical chemistry.Aimed at different application fields,many subjects such as in vivo analysis and environmental analysis are derived.In all areas of application,there are difficulties in how to eliminate interferences,how to improve the target signal and so on.Therefore,sample pretreatment is very important in analysis detection,which takes up 60%of the whole analysis time and often causes deviations.In order to promote the development of sample pretreatment techniques and solve more analytical problems,we prepared different functionalized ILs composites in this work.They are applied in SPE and combined with other analytic instruments,realizing the detection of neurotransmitters in vivo,carcinogenic substances in stationery,antibiotics and anesthetic drugs in clinical medicine,which lays a solid theoretical and application foundation for the wide range of research and application in the environment,life sciences and clinical medicine and other fieldsChapter 1.OverviewThis chapter mianly introduces the development of ILs since its introduction in 1914.As a kind of green solvent,IL has been applied in many areas.SPE has been widely used in pretreating complex samples because of its unique advantages.However,how to select and prepare SPE packings are the main problems of SPE's development.This chapter also introduces functionalized IL materials' application in SPE which provides a new way to solve the above problems.Finally,the author illustrates the purpose of this research,the main contents,the innovations and the main significances of this study.Chapter 2.Study of amino-functionalized ionic liquids modified graphene oxide and its application for solid phase extraction and determination for phthalates in erasersIn this study,we prepared four novel GO composites based on ILs which are functionalized with amino-group for solid phase extraction of specific targeted molecules,which overcome the drawbacks of traditional GO adsorbent,such as high column pressure,damaged easily and hard to separate from liquid phase.Moreover,they remain the advantages of GO,such as large specific surface area and execellent adsorption capacity.Combining with the research on the structure and properties of target molecules,we designed the structure of ILs which can selectively extract different analytes.In 2015,it was reported that the content of PAE contained in stationery exceeded the standard limit in Jangsu Province.Based on this report,we applied these composites to extract and detect nine PAEs from eraser samples.By comparing the extraction effect of four GO composites(GO-[AEMIM][Br]achieving the best result),we found that if we change the structure of IL and the extraction condition(such as pH,salt concentration,etc.),we can change the enrichment performance significantly.This provides us a solid theoretical and data support to explore the design of specific functionalized ILs and the optimization of different extraction conditions.Chapter 3.Study and application of crosslinked polymeric ionic liquid column for the extraction efficiency of catecholaminesIn this work,we used 1-propylpheny 1-3-vinyl imidazolium chloride as IL monomer and divinylbenzene as crosslinking agent to synthetize a novel crosslinked polymeric ionic liquids.This polymer has good stability,high pressure resistance,high mechanical strength and shows good ability of adsorbing DPBA.Based on this polymer,we prepared the novel SPE column whose inner diameter is 0.9mm,which can pretreat trace sample in life science.Basd on that the ortho-phenolic hydroxyl group of catecholamine can form two B-O bonds with B atom,the SPE column can selectively extract catecholamine with high sensitivity and adsorption capacity.We combined the prepared solid phase column with microdialysis sampling technique to detect the catecholamine in rat blood.Thus,we avoided impurities influcing the detection and improve the detection limit of catecholamines.This method covered the calibration range from 0.2ng/mL to 300ng/mL and more importantly,reduced the amount of sample greatly(5-40 ?L),which improved the time resolution in-vivo analysis and provided a new method for the further diagnosis in human diseases.Chapter 4.Extraction and detection for vancomycin in rat blood based on alky chain-functionalized ionic liquids modified solid phase extraction fiberVancomycin is a kind of glycopeptide antibiotics which has a strong effect of sterilization.However,it has a certain nephrotoxicity and ototoxicity.Especially its nephrotoxicity is highly related to its content in blood.Therefore,it is necessary to realize real-time and rapid monitoring of vancomycin concentration in ICU so that we can adjust the concentration and reduce its side effects.Combining with our previous studies,we synthetized 1-hexadecyl-3-vinylimidazolium bis(trifluoromethylsulfonyl)imide which had double bond and hydrophobic alkyl chain in this work.The IL was polymerized with the double bond on the surface of fused silica capillary to form the composite coating.The surface of the coating was very smooth and stable.The prepared fiber was applied to the detection of vancomycin in the blood,which not only reduced the volume of sample,but also eliminated the interferences of protein matrix and red blood cells.Besides,the time of extraction and analysis is quite short when using the fiber.As a kind of green material with good biocompatibility,IL has a good prospect in clinical application.Chapter 5.Dynamic real-time monitoring of propofol injection in rat blood based on crosslinked polymeric ionic liquids modified solid phase extraction fiberIn the work,we mixed IL monomer,IL crosslinker and the photo-initiator DAROCUR 1173 together.Then they were exposed to 360 nm UV light to realize the IL bonding with the double bond on the surface of fused silica capillary.Thus,we made the solid-phase extraction fiber based on crosslinked PIL coatings.The thickness of the fiber can be limited to 1mm.The fiber was applied to extract propofol in the blood of SD rats.Combining with HPLC-UV,we can easily know the exact concentration of propofol through only two steps,extraction and detection.This method has a high anti-interference ability,and not need cumbersome sample pretreatment,which can greatly improve the biological sample analysis of the time resolution.Finally,we achieved real-time online analysis of the targeted molecules,which is expected to be applied to the dynamic real-timely monitor propofol injection in clinical operation.We will play a positive role in solving the problem of traditional drug delivery in surgery and the implementation of precision diagnosis. |
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