https://dx.doi.org/10.4322/sc.2012.004
Dispersive liquid-liquid microextraction (DLLME): fundamentals and applications
Martins, Manoel Leonardo; Primel, Ednei Gilberto; Caldas, Sergiane Souza; Prestes, Osmar Damian; Adaime, Martha Bohrer; Zanella, Renato
Palavras-chave: Sample preparation, miniaturized extraction, organic compounds, chromatography.
Resumo: In the last years, the classical sample preparation techniques for the determination of organic compounds in environmental and food samples are being replaced by miniaturized techniques that are characterized by low cost, high efficiency, low solvents consume, with the possibility of automation. Among these techniques, the Dispersive Liquid-Liquid Microextraction (DLLME) presents an interesting alternative for sample preparation and is based in the partition of analytes using a mixture of solvents (disperser and extractor). The DLLME presents as main advantages the miniaturization, low cost, the speed, the efficiency of extraction and preconcentration, as well as the potential for direct application in the field. This review presents the fundamentals and recent applications of DLLME in the analysis of organic compounds in different samples.
Referências Bibliográficas
1. Ojeda CB, Rojas FS. Separation and Preconcentration by Dispersive Liquid-Liquid Microextraction Procedure: Recent Applications. Chromatographia 2011; 74:651- 679.. https://dx.doi.org/10.1007/s10337-011-2124-1
2. Rezaee M, Assadi Y, Hossein MM, Aghaee E, Ahmadia F, Berijani S. Determination of organic compounds in water using dispersive liquid-liquid microextraction. Journal Chromatography A 2006; 1116:1-9. https:// dx.doi.org/10.1016/j.chroma.2006.03.007
3. Rezaee M, Yamini Y, Faraji M. Evolution of dispersive liquid-liquid microextraction method. Journal of Chromatography A 2010; 1217:2342-2357. https:// dx.doi.org/10.1016/j.chroma.2009.11.088
4. Yazdi AS, Amiri A. Liquid-phase microextraction. Trends in Analytical Chemistry 2010; 29(1):1-14. https://dx.doi.org/10.1016/j.trac.2009.10.003
5. Berijani S, Assadi Y, Anbia M, Hosseini MRM, Aghaee E. Dispersive liquid-liquid microextraction combined with gas chromatography-flame photometric detection Very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water. Journal of Chromatography A 2006; 1123:1-9. https://dx.doi.org/10.1016/j.chroma.2006.05.010
6. Oliveira ARM, Magalhães IRS, Santana FJM, Bonato PS. Microextração em Fase Líquida (LPME): Fundamentos da técnica e aplicações na análise de fármacos em fluidos biológicos. Química Nova 2008; 31(3):637-644. https://dx.doi.org/10.1590/ S0100-4042200800030003
7. Harris DC. Análise Química Quantitativa. 8th ed. Rio de Janeiro: LTC; 2012. 886 p.
8. Bjergaard SP, Rasmussen KE. Liquid-phase microextraction with porous hollow fibers, a miniaturized and highly flexible format for liquid-liquid extraction. Journal Chromatography A 2008; 1184:132-142. https://dx.doi.org/10.1016/j. chroma.2007.08.088
9. Ho TS, Vasskog T, Anderssen T, Jensen E, Rasmussen KE, Bjergaard SP. 25,000-fold pre-concentration in a single step with liquid-phase microextraction. Analytica Chimica Acta 2007; 592:1-8. https://dx.doi. org/10.1016/j.aca.2007.04.014
10. Kozani RR, Assadi Y, Shemirani F, Hosseini MRM, Jamali MR. Part-per-trillion determination of chlorobenzenes in water using dispersive liquid-liquid microextraction combined gaschromatography electron capture detection. Talanta 2007; 72:387-393. https://dx.doi.org/10.1016/j.talanta.2006.10.039
11. Herrera-Herrera AV, Asensio-Ramos M, Hernandez- Borges J, Rodriguez-Delgado MA. Dispersive liquid-liquid microextraction for determination of organic analytes. Trends in Analytical Chemistry 2010; 29(7):728-751. https://dx.doi. org/10.1016/j.trac.2010.03.016
12. Zang XH, Wu QH, Zhang MY, Xi GH, Wang S. Developments of Dispersive Liquid-Liquid Microextraction Technique. Chinese Journal of Analytical Chemistry 2009; 37(2):161-168. https:// dx.doi.org/10.1016/S1872-2040(08)60082-1
13. Merck Chemicals. Solventes para Cromatografia Líquida. Lichrosolv. [cited feb 2012]. Available from: https://www.merck-chemicals.com/brazil/ copy-of-solventes-para-cromatografia-liquidalichrosolv-/ c_3xab.s1OK68AAAEuBEdQn6U9.
14. Anthemidis AN, Ioannou KIG. Recent developments in homogeneous and dispersive liquid-liquid extraction for inorganic elements determination. A review. Talanta 2009; 80:413-421. https://dx.doi. org/10.1016/j.talanta.2009.09.005
15. Liu L, Cheng J, Matsadiq G, Zhou H, Li J. Application of DLLME to the Determination of Pyrethroids in Aqueous Samples. Chromatographia 2010; 72:1017- 1020.. https://dx.doi.org/10.1365/ s10337-010-1732-5 0009-5893/10/11
16. Leong M, Huang S. Dispersive liquid-liquid microextraction method based on solidification of floating organic drop combined with gas chromatography with electron-capture or mass spectrometry detection. Journal of Chromatography A 2008; 1211:8-12. https://dx.doi.org/10.1016/j. chroma.2008.09.111
17. Leong MI, Chang CC, Fuh MR, Huang SD. Low toxic dispersive liquid-liquid microextraction using halosolvents for extraction of polycyclic aromatic hydrocarbons in water samples. Journal of Chromatography A 2010; 1217:5455-5461. https:// dx.doi.org/10.1016/j.chroma.2010.06.056
18. Krylov VA, Krylov AV, Mosyagin PV, Matkivskaya YO. Liquid-Phase Microextraction Preconcentration of Impurities. Journal of Analytical Chemistry 2011; 66(4):331-350. https://dx.doi. org/10.1134/S1061934811040101
19. Hadjmohammadi MR, Ghoreishi SS. Determination of Estrogens in Water Samples Using Dispersive Liquid Liquid Microextraction and High Performance Liquid Chromatography. Acta Chimica Slovenica 2011; 58:765-771.
20. Nagaraju D, Huang SD. Determination of triazine herbicides in aqueous samples by dispersive liquidliquid microextraction with gas chromatography-ion trap mass spectrometry. Journal of Chromatography A 2007; 1161:89-97. https://dx.doi.org/10.1016/j. chroma.2007.05.065
21. Caldas SS, Gonçalves FF, Primel EG, Prestes OD, Martins ML, Zanella R. Principais técnicas de preparo de amostra para a determinação de resíduos de agrotóxicos em água por cromatografia líquida com detecção por arranjo de diodos e por espectrometria de massas. Química Nova 2011; 34(9):1604-1617. https://dx.doi.org/10.1590/S0100-40422011000900021
22. Farhadi K, Matin AA, Hashemi P. LC Determination of Trace Amounts of Phenoxyacetic Acid Herbicides in Water after Dispersive Liquid-Liquid Microextraction. Chromatographia 2009; 69:45-49. https://dx.doi. org/10.1365/s10337-008-0815-z0009-5893/09/01
23. Chou T, Lin S, Fuh M. Determination of phenylurea herbicides in aqueous samples using partitioned dispersive liquid-liquid microextraction. Talanta 2009; 80:493-498. https://dx.doi.org/10.1016/j. talanta.2009.07.005
24. López-Darias J, Pino V, Ayala JH, Afonso AM. In-situ ionic liquid-dispersive liquid-liquid microextraction method to determine endocrine disrupting phenols in seawaters and industrial effluents. Microchimica Acta 2011; 174:213-222. https://dx.doi.org/10.1007/ s00604-011-0636-x
25. Ye Q, Zheng D, Liu L, Hong L. Rapid analysis of aldehydes by simultaneous microextraction and derivatization followed by GC-MS. Journal of Separation Science 2011; 34:1607-1612. https://dx.doi. org/10.1002/jssc.201100145
26. Sobhi HR, Farahani H, Kashtiaray A, Farahani MR. Tandem use of solid-phase extraction and dispersive liquid-liquid microextraction for the determination of mononitrotoluenes in aquatic environment. Journal of Separation Science 2011; 34:1035-1040. https://dx.doi. org/10.1002/jssc.201000529
27. Martín J, Buchberger W, Alonso E, Himmelsbach M, Aparicio I. Comparison of different extraction methods for the determination of statin drugs in wastewater and river water by HPLC/Q-TOF-MS. Talanta 2011; 85:607-615. https://dx.doi.org/10.1016/j. talanta.2011.04.017
28. Guo J, Li X, Cao X, Li Y, Wang X, Xu X. Determination of triclosan, triclocarban and methyl-triclosan in aqueous samples by dispersive liquid-liquid microextraction combined with rapid liquid chromatography. Journal of Chromatography A 2009; 1216:3038-3043. https:// dx.doi.org/10.1016/j.chroma.2009.02.021
29. Herrera-Herrera AV, Hernandez-Borges J, Borges- Miquel T, Rodriguez-Delgado MA. Dispersive liquid-liquid microextraction combined with nonaqueous capillary electrophoresis for the determination of fluoroquinolone antibiotics in Waters. Electrophoresis 2010; 31:3457-3465. https:// dx.doi.org/10.1002/elps.201000285
30. Saraji M., Boroujeni MK, Bidgoli AAH. Comparison of dispersive liquid-liquid microextraction and hollow fiber liquid-liquid-liquid microextraction for the determination of fentanyl, alfentanil, and sufentanil in water and biological fluids by highperformance liquid chromatography. Analytical and Bioanalytical Chemistry 2011; 400:2149-2158. https:// dx.doi.org/10.1007/s00216-011-4874-x
31. Wen Y, Li J, Zhang W, Chen L. Dispersive liquidliquid microextraction coupled with capillary electrophoresis for simultaneous determination of sulfonamides with the aid of experimental design. Electrophoresis 2011; 32:2131-2138. https://dx.doi. org/10.1002/elps.201100142
32. Caldas SS, Costa FP, Primel EG. Validation of method for determination of different classes of pesticides in aqueous samples by dispersive liquid liquid microextraction with liquid chromatography tandem mass spectrometric detection. Analytica Chimica Acta 2010; 32:55-62 https://dx.doi.org/10.1016/j. aca.2010.03.004
33. Chen H, Chen R, Li S. Low-density extraction solventbased solvent terminated dispersive liquid-liquid microextraction combined with gas chromatographytandem mass spectrometry for the determination of carbamate pesticides in water samples. Journal of Chromatography A 2010; 1217:1244-1248. https:// dx.doi.org/10.1016/j.chroma.2009.12.062
34. He L; Luo X; Jiang X, Qu L. A new 1,3-dibutylimidazolium hexafluorophosphate ionic liquid-based dispersive liquid-liquid microextraction to determine organophosphorus pesticides in water and fruit samples by high-performance liquid chromatography. Journal of Chromatography A 2010; 1217:5013-5020. https://dx.doi.org/10.1016/j.chroma.2010.05.057
35. Zhao R, Wang X, Li F, Wang S, Zhang L, C Cheng. Ionic liquid/ionic liquid dispersive liquid- liquid microextraction. Journal of Separation Science 2011; 34:830-836. https://dx.doi.org/10.1002/ jssc.201000802
36. Farajzadeh MA, Bahram M, Vardast MR. Central Composite Design Applied to Optimization of Dispersive Liquid-Liquid Microextraction of Cu(II) and Zn(II) in Water Followed by High Performance Liquid Chromatography Determination. CLEAN - Soil, Air, Water 2010; 38(5-6):466-477. https://dx.doi.org/10.1002/clen.200900257
37. Asensio-Ramos M, Hernandez-Borges J, Borges- Miquel TM, Rodriguez-Delgado MA. Ionic liquid-dispersive liquid-liquid microextraction for the simultaneous determination of pesticides and metabolites in soils using high-performance liquid chromatography and fluorescence detection. Journal of Chromatography A 2011; 1218:4808-4816. https:// dx.doi.org/10.1016/j.chroma.2010.11.030
38. Liu X, Zhao A, Zhang A, Liu H, Xiao W, Wang C et al. Dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry determination of polychlorinated biphenyls and polybrominated diphenyl ethers in milk. Journal of Separation Science 2011; 34:1084-1090. https://dx.doi.org/10.1002/ jssc.201000767
39. Hu Y, Li Y, Zhang W, Wang H, Huang C, Zhang M et al. Dispersive liquid-liquid microextraction followed by gas chromatography-electron capture detection for determination of polychlorinated biphenyls in fish. Journal of Separation Science 2009; 32:2103-2108. https://dx.doi.org/10.1002/jssc.200900027
40. Moinfar S, Hosseini MRM. Development of dispersive liquid-liquid microextraction method for the analysis of organophosphorus pesticides in tea. Journal of Hazardous Materials 2009; 169:907-911. https://dx.doi. org/10.1016/j.jhazmat.2009.04.030
41. Yang P, Ren H, Qiu H, Liu X, Jiang S. Determination of four trace preservatives in street food by ionic liquidbased dispersive liquid-liquid micro-extraction. Chemical Papers 2011; 65(6):747-753. https://dx.doi. org/10.2478/s11696-011-0071-9
42. Fu L, Liu X, Hu J, Zhao X, Wang H, Wang X. Application of dispersive liquid-liquid microextraction for the analysis of triazophos and carbaryl pesticides in water and fruit juice samples. Analitica Chemica Acta 2009; 632:289-295. https://dx.doi.org/10.1016/j. aca.2008.11.020
43. Daneshfar A, Khezeli T, Lotfi HJ. Determination of cholesterol in food samples using dispersive liquid liquid microextraction followed by HPLC-UV. Journal of Chromatography B 2009; 877:456-460. https://dx.doi. org/10.1016/j.jchromb.2008.12.050
44. Zhao E, Zhao W, Han L, Jiang S, Zhou Z. Application of dispersive liquid-liquid microextraction for the analysis of organophosphorus pesticides in watermelon and cucumber. Journal of Chromatography A 2007; 1175:137-140. https://dx.doi.org/10.1016/j. chroma.2007.10.069
45. Cabo TR, Rodríguez I, Ramil M, Cela R. Dispersive liquid-liquid microextraction using non-chlorinated, lighter than water solvents for gas chromatography-mass spectrometry determination of fungicides in wine. Journal of Chromatography A 2011; 1218:6603-6611. https://dx.doi.org/10.1016/j. chroma.2011.07.054
46. Campillo N, Viñas P, Cacho JI, Peñalver R, Córdoba MH. Evaluation of dispersive liquidliquid microextraction for the simultaneous determination of chlorophenols and haloanisoles in wines and cork stoppers using gas chromatographymass spectrometry. Journal of Chromatography A 2010; 1217:7323-7330. https://dx.doi.org/10.1016/j. chroma.2010.09.058
47. Cunha SC, Fernandes JO, Oliveira MBPP. Fast analysis of multiple pesticide residues in apple juice using dispersive liquid-liquid microextraction and multidimensional gas chromatographymass spectrometry. Journal of Chromatography A 2009; 1216:8835-8844. https://dx.doi.org/10.1016/j. chroma.2009.10.051
48. Fu L, Liu X, Hu J, Zhao X, Wang H, Wang X. Application of dispersive liquid-liquid microextraction for the analysis of triazophos and carbaryl pesticides in water and fruit juice samples Analityca Chimica Acta 2009; 632:289-295. https://dx.doi.org/10.1016/j. aca.2008.11.020
49. Han Y, Jia X, Liu X, Duan T, Chen H. DLLME Combined with GC-MS for the Determination of Methylparaben, Ethylparaben, Propylparaben and Butylparaben in Beverage Samples. Chromatographia 2010; 72:351-355. https://dx.doi. org/10.1365/s10337-010-1646-2 0009-5893/10/08
50. Wang Y, You J, Ren R, Xiao Y, Gao S, Zhang H et al. Determination of triazines in honey by dispersive liquid-liquid microextraction high-performance liquid chromatography. Journal of Chromatography A 2010; 1217:4241-4246. https://dx.doi.org/10.1016/j. chroma.2010.03.031
51. Farajzadeh MA, Djozan D, Mogaddan MRA. Extraction and preconcentration technique for triazole pesticides from cow milk using dispersive liquid-liquid microextraction followed by GC-FID and GC-MS determinations. Journal of Separations Science 2011; 34:1309-1316. https://dx.doi.org/10.1002/ jssc.201000928
52. Fariña L, Boido E, Carrau F, Delacassa E. Determination of volatile phenols in red wines by dispersive liquidliquid microextraction and gas chromatography-mass spectrometry detection. Journal of Chromatography A 2007;1157:46-50. https://dx.doi.org/10.1016/j. chroma.2007.05.006
53. Yan H, Wang H, Qiao J, Yang G. Molecularly imprinted matrix solid-phase dispersion combined with dispersive liquid-liquid microextraction for the determination of four Sudan dyes in egg yolk. Journal of Chromatography A 2011; 1218:2182-2188 https:// dx.doi.org/10.1016/j.chroma.2011.02.042
54. Chen H, Ding W, Determination of aqueous fullerene aggregates in water by ultrasoundassisted dispersive liquid-liquid microextraction with liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry. Journal of Chromatography A 2012; 1223:15-23. https://dx.doi. org/10.1016/j.chroma.2011.12.034
55. Andruch V, Acebal CC, Jkrlikova J, Sklenatova H, Solich P, Balogh IS et al. Automated on-line dispersive liquid-liquid microextraction based on a sequential injection system. Microchemical Journal 2012; 100:77- 82.. https://dx.doi.org/10.1016/j.microc.2011.09.006
56. Maya F, Estela JM, Cerdà V. Completely automated in-syringe dispersive liquid-liquid microextraction using solvents lighter than water. Analytical and Bioanalytical Chemistry 2012; 402:1383-1388. https:// dx.doi.org/10.1007/s00216-011-5572-4
57. Grzeskowiak AZ, Grzeskowiak T. Dispersive liquid-liquid microextraction. Trends in Analytical Chemistry 2011; 30(9):1382-1399. https://dx.doi. org/10.1016/j.trac.2011.04.014
58. Asensio-Ramos M, Revelo-Perez LM, González- Curbelo MA, Hernandez-Borges J. Liquid phase microextraction applications in food analysis. Journal of Chromatography A 2011; 1218:7415-7437. https:// dx.doi.org/10.1016/j.chroma.2011.05.096
59. Ebrahimzadeh H, Abedi H, Yamini Y, Adlnasab L. Molecular-imprinted polymer extraction combined with dispersive liquid-liquid micro-extractionfor ultra-preconcentration of mononitrotoluene. Journal of Separation Science 2010; 33:3759-3766. https:// dx.doi.org/10.1002/jssc.201000376
60. Luo YB, Shi ZG, Gao Q, Fenga YQ. Magnetic retrieval of graphene: Extraction of sulfonamide antibiotics from environmental water samples. Journal of Chromatography A 2011; 1218:1353-1358. https:// dx.doi.org/10.1016/j.chroma.2011.01.022.