Single drop microextraction (SDME): fundamentals and applications

Pinto, Iohana Pinto de; Pedroso, Marcio Pozzobon

Palavras-chave: samples preparation, liquid phase microextraction, chromatography, single drop.

Resumo: The classical sample preparation techniques are being replaced by miniaturized techniques due to low cost, low solvents consume and possibility of automation. The first liquid phase microextraction technique developed was the single drop microextraction (SDME) and since then new operation modes have been developed. The SDME principle is based on partition of the analytes between the sample and a small drop of an organic solvent. Theoretical principles, operation modes and recent applications of the SDME in the determination of organic compounds by chromatographic techniques are presented in this review.

Referências Bibliográficas

1. Chen Y, Guo Z, Wang X, Qiu C. Sample preparation. Journal of Chromatography A. 2008;1184(1-2):191–219.
2. Lanças FM. Avanços Recentes e Tendências Futuras das Técnicas de Separação : uma visão pessoal. Scientia Chromatographica. 2008;17–44.
3. Psillakis E, Kalogerakis N. Developments in single-drop microextraction. Trends in Analytical Chemistry. 2002;21(1):53–63.
4. Arthur C, Pawlyszin J. Solid phase microextraction with thermal desorption using fused silica optical fibers. Analytical Chemistry. 1990;62(19):2145–8.
5. Pawliszyn J. Sample preparation: Quo vadis? Analytical Chemistry. 2003;75(11):2543–58.
6. Moreira BJ, Yokoya JMC, Gaitani CM de. Microextração líquido-líquido dispersiva (DLLME): fundamentos, inovações e aplicações biológicas. Scientia Chromatographica. 2015;6(3):186–204.
7. Hu B, He M, Chen B, Xia L. Liquid phase microextraction for the analysis of trace elements and their speciation. Spectrochimica Acta – Part B Atomic Spectroscopy.; 2013;86:14–30.
8. Jeannot M a, Cantwell FF. Solvent microextraction into a single drop. Analytical Chemistry. 1996;68(13):2236–40.
9. He Y, Lee HK. Liquid-phase microextraction in a single drop of organic solvent by using a conventional microsyringe. Analytical Chemistry. 1997;69(22):4634–40.
10. Cortada C, Vidal L, Tejada S, Romo A, Canals A. Determination of organochlorine pesticides in complex matrices by single-drop microextraction coupled to gas chromatography–mass spectrometry. Analytica Chimica Acta. 2009 ;638(1):29–35.
11. Yu Y, Chen B, Shen C, Cai Y, Xie M, Zhou W, et al. Multiple headspace single-drop microextraction coupled with gas chromatography for direct determination of residual solvents in solid drug product. Journal of Chromatography A. 2010;1217(32):5158–64.
12. Jager LS, Andrews a. RJ. Solvent microextraction of chlorinated pesticides. Chromatographia. 1999;50(11-12):733–8.
13. Šrámková I, Horstkotte B, Solich P, Sklenářová H. Automated in-syringe single-drop head-space micro-extraction applied to the determination of ethanol in wine samples. Analytica Chimica Acta. 2014;828:53–60.
14. Xia L, Hu B, Jiang Z, Wu Y, Li L, Chen R. 8-Hydroxyquinoline-chloroform single drop microextraction and electrothermal vaporization ICP-MS for the fractionation of aluminium in natural waters and drinks. Journal of Analytical Atomic Spectrometry. 2005;20(5):441.
15. Jeannot MA, Przyjazny A, Kokosa JM. Single drop microextraction-development, applications and future trends. Journal of chromatography A. 2010 ;1217(16):2326–36.
16. Kokosa JM. Advances in solvent-microextraction techniques. Trends in Analytical Chemistry. 2013;43:2–13.
17. Jain A, Verma KK. Recent advances in applications of single-drop microextraction: A review. Analytica Chimica Acta. 2011;706(1):37–65.
18. Agostinho AD. FM. Determinação do coeficiente de distribuição (Kd) de Benzo(A)pireno em solo por isotermas de sorção. Química Nova. 2006;29(4):657–61.
19. Borges, B. K.; Figueiredo, C. E.; Queiroz CME. Preparo de amostras para análise de compostos orgânicos. 1st ed. GEN, editor. Rio de Janeiro: Editora LTC; 2015.
20. Sarafraz Yazdi A, Razavi N. Separation and determination of amitriptyline and nortriptyline in biological samples using single- drop microextraction with GC. Chromatographia. 2011;73(5-6):549–57.
21. Jeannot M a., Cantwell FF. Mass transfer characteristics of solvent extraction into a single drop at the tip of a syringe needle. Analytical Chemistry. 1997;69(2):235–9.
22. Xu J, Liang P, Zhang T. Dynamic liquid-phase microextraction of three phthalate esters from water samples and determination by gas chromatography. Analytica Chimica acta. 2007;597(1):1–5.
23. Theis AL, Waldack AJ, Hansen SM, Jeannot MA. Headspace solvent microextraction. Analytical Chemistry. 2001;73(23):5651–4.
24. Rincón A a., Pino V, Ayala JH, Afonso AM. Headspace-single drop microextraction (HS-SDME) in combination with high- performance liquid chromatography (HPLC) to evaluate the content of alkyl- and methoxy-phenolic compounds in biomass smoke. Talanta. 2011;85(3):1265–73.
25. Shen G, Lee HK. Headspace liquid-phase microextraction of chlorobenzenes in soil with gas chromatography-electron capture detection. Analytical Chemistry. 2003;75(1):98–103.
26. Xu L, Basheer C, Lee HK. Developments in single-drop microextraction. Journal of Chromatography A. 2007;1152(1-2):184–92.
27. Liu W, Lee HK. Continous flow microextraction exceeding 1000-fold concentration of dilute analytes. Analytical Chemistry. 2000;72(18):4462–7.
28. Li Y, Zhang T, Liang P. Application of continuous-flow liquid-phase microextraction to the analysis of volatile halohydrocarbons in water. Analytica Chimica Acta. 2005;536(1-2):245–9.
29. Ho TS, Pedersen-Bjergaard S, Rasmussen KE. Recovery, enrichment and selectivity in liquid-phase microextraction: Comparison with conventional liquid-liquid extraction. Journal of Chromatography A. 2002;963(1-2):3–17.
30. Yangcheng L, Quan L, Guangsheng L, Youyuan D. Directly suspended droplet microextraction. Analytica Chimica Acta. 2006 May;566(2):259–64.
31. Khalili Zanjani MR, Yamini Y, Shariati S, Jönsson JA. A new liquid-phase microextraction method based on solidification of floating organic drop. Analytica chimica acta. 2007;585(2):286–93.
32. Kokosa JM. Recent trends in using single-drop microextraction and related techniques in green analytical methods. Trends in Analytical Chemistry. 2015;71:194–204.
33. Jahan S, Xie H, Zhong R, Yan J, Xiao H, Fan L, et al. A highly efficient three-phase single drop microextraction technique for sample preconcentration. The Analyst. 2015;140:3193–200.
34. López-Blanco C, Gómez-Álvarez S, Rey-Garrote M, Cancho-Grande B, Simal-Gándara J. Determination of carbamates and organophosphorus pesticides by SDME-GC in natural water. Analytical and Bioanalytical Chemistry. 2005;383(4):557–61.
35. Przyjazny A, Kokosa JM. Analytical characteristics of the determination of benzene, toluene, ethylbenzene and xylenes in water by headspace solvent microextraction. Journal of Chromatography A. 2002;977(2):143–53.
36. Amde M, Tan Z-Q, Liu R, Liu J-F. Nanofluid of zinc oxide nanoparticles in ionic liquid for single drop liquid microextraction of fungicides in environmental waters prior to high performance liquid chromatographic analysis. Journal of Chromatography A. 2015;1395:7–15.
37. Zhang M, Huang J, Wei C, Yu B, Yang X, Chen X. Mixed liquids for single-drop microextraction of organochlorine pesticides in vegetables. Talanta. 2008;74(4):599–604.
38. Wardencki W, Curyło J, Namieśnik J. Trends in solventless sample preparation techniques for environmental analysis. Journal of Biochemical and Biophysical Methods. 2007;70(2):275–88.
39. Bendicho C, Costas-Mora I, Romero V, Lavilla I. Nanoparticle-enhanced liquid-phase microextraction.Trends in Analytical Chemistry. 2015;68:78–87.
40. Aguilera-Herrador E, Lucena R, Cárdenas S, Valcárcel M. The roles of ionic liquids in sorptive microextraction techniques. Trends in Analytical Chemistry. 2010;29(7):602–16.
41. De Souza Pinheiro A, de Andrade JB. Development, validation and application of a SDME/GC-FID methodology for the multiresidue determination of organophosphate and pyrethroid pesticides in water. Talanta. 2009;79(5):1354–9.
42. Pinheiro ADS, da Rocha GO, De Andrade JB. A SDME/GC-MS methodology for determination of organophosphate and pyrethroid pesticides in water. Microchemical Journal. 2011;99(2):303–8.
43. Martendal E, Budziak D, Carasek E. Application of fractional factorial experimental and Box-Behnken designs for optimization of single-drop microextraction of 2,4,6-trichloroanisole and 2,4,6-tribromoanisole from wine samples. Journal of chromatography A. 2007;1148(2):131–6.
44. Kaykhaii M, Abdi A. Rapid and sensitive determination of acrylamide in potato crisps using reversed-phase direct immersion single drop microextraction-gas chromatography. Analytical Methods. 2013;5(5):1289.
45. Batlle R, López P, Nerín C, Crescenzi C. Active single-drop microextraction for the determination of gaseous diisocyanates. Journal of Chromatography A. 2008;1185(2):155–60.
46. Aguilera-Herrador E, Lucena R, Cardenas S, Valcárcel M. Direct coupling of ionic liquid based single-drop microextraction and GC/MS. Analytical Chemistry. 2008;80(3):793–800.
47. Aguilera-Herrador E, Lucena R, Cárdenas S, Valcárcel M. Ionic liquid-based single-drop microextraction/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene and xylene isomers in waters. Journal of Chromatography A. 2008;1201(1):106–11.
48. Zhao F-Q, Li J, Zeng B-Z. Coupling of ionic liquid-based headspace single-drop microextraction with GC for sensitive detection of phenols. Journal of separation science. 2008;31(16-17):3045–9.
49. Spietelun A, Marcinkowski Ł, De La Guardia M, Namieśnik J. Green aspects, developments and perspectives of liquid phase microextraction techniques. Talanta. 2014;119:34–45.
50. Ye C-L, Zhou Q-X, Wang X-M. Headspace liquid-phase microextraction using ionic liquid as extractant for the preconcentration of dichlorodiphenyltrichloroethane and its metabolites at trace levels in water samples. Analytica Chimica Acta. 2006;572(2):165–71.
51. Ye C, Zhou Q, Wang X, Xiao J. Determination of phenols in environmental water samples by ionic liquid-based headspace liquid-phase microextraction coupled with high-performance liquid chromatography. Journal of Separation Science. 2007;30(1):42–7.
52. Vidal L, Chisvert A, Canals A, Salvador A. Sensitive determination of free benzophenone-3 in human urine samples based on an ionic liquid as extractant phase in single-drop microextraction prior to liquid chromatography analysis. Journal of Chromatography A. 2007;1174(1-2):95–103.
53. Liu J-F, Peng J-F, Chi Y-G, Jiang G-B. Determination of formaldehyde in shiitake mushroom by ionic liquid-based liquid-phase microextraction coupled with liquid chromatography. Talanta. 2005;65(3):705–9.
54. Wen X, Deng Q, Wang J, Yang S, Zhao X. A new coupling of ionic liquid based-single drop microextraction with tungsten coil electrothermal atomic absorption spectrometry. Spectrochimica Acta – Part A: Molecular and Biomolecular Spectroscopy. 2013;105:320–5.
55. Č abala R, Bursová M. Bell-shaped extraction device assisted liquid-liquid microextraction technique and its optimization using response-surface methodology. Journal of Chromatography A. 2012;1230:24–9.
56. Li X, Xue A, Chen H, Li S. Low-density solvent-based dispersive liquid-liquid microextraction combined with single-drop microextraction for the fast determination of chlorophenols in environmental water samples by high performance liquid chromatography-ultraviolet detection. Journal of Chromatography A. 2013;1280:9–15.
57. Ouyang G, Zhao W, Pawliszyn J. Automation and optimization of liquid-phase microextraction by gas chromatography. Journal of Chromatography A. 2007;1138(1-2):47–54.
58. Williams DBG, George MJ, Meyer R, Marjanovic L. Bubbles in solvent microextraction: the influence of intentionally introduced bubbles on extraction efficiency. Analytical Chemistry. 2011;83(17):6713–6.
59. Williams DBG, George MJ, Marjanovic L. Rapid detection of atrazine and metolachlor in farm soils: gas chromatography-mass spectrometry-based analysis using the bubble-in-drop single drop microextraction enrichment method. Journal of agricultural and Food Chemistry. American Chemical Society; 2014;62(31):7676–81.
60. Pereira AC, Rocha FRP. Liquid-liquid microextraction in a multicommuted flow system for direct spectrophotometric determination of iodine value in biodiesel. Analytica Chimica Acta. 2014;829:28–32.
61. Fang C, Xiong Y, Liang Q, Li Y, Peng P. Optimization of headspace single-drop microextraction technique for extraction of light hydrocarbons (C6-C12) and its potential applications. Organic Geochemistry. 2011;42(4):316–22.
62. Hashemi M, Habibi A, Jahanshahi N. Determination of cyclamate in artificial sweeteners and beverages using headspace single-drop microextraction and gas chromatography flame-ionisation detection. Food Chemistry. 2011;124(3):1258–63.
63. Vallecillos L, Pocurull E, Borrull F. Fully automated ionic liquid-based headspace single drop microextraction coupled to GC-MS/MS to determine musk fragrances in environmental water samples. Talanta. 2012;99:824–32.
64. Gholivand MB, Piryaei M. A method for fast analysis of volatile components of Citrus aurantium L. leaves. Natural Product Research. 2013;27(14):1315–8.
65. Tang B, Tian M, Row KH. Determination of terpenoids in Chamaecyparis obtusa Leaves by headspace single-drop microextraction with gas chromatography detection. Analytical Letters. 2013;47(1):48–57.
66. Enteshari M, Mohammadi A, Nayebzadeh K, Azadniya E. Optimization of headspace single-drop microextraction coupled with gas chromatography-mass spectrometry for determining volatile oxidation compounds in mayonnaise by response surface methodology. Food Analytical Methods. 2014;7(2):438–48.
67. Jiang C, Wei S, Li X, Zhao Y, Shao M, Zhang H, et al. Ultrasonic nebulization headspace ionic liquid-based single drop microextraction of flavour compounds in fruit juices. Talanta. 2013;106:237–42.
68. Kaykhaii M, Ghalehno MH. Rapid and sensitive determination of fluoride in toothpaste and water samples using headspace single drop microextraction-gas chromatography. Analitycall Methods. 2013;5(20):5622–6.
69. Yu J, Zhao C, Chong F, Cao Y, Subhan F, Cui B, et al. A simple, rapid and eco-friendly approach for the analysis of aromatic amines in environmental water using single-drop microextraction – gas chromatography. Journal of Chromatographic Science. 2015;53(2):360–5.
70. Tian F, Liu W, Fang H, An M, Duan S. Determination of six organophosphorus pesticides in water by single-drop microextraction coupled with GC-NPD. Chromatographia. 2013;77(5-6):487–92.
71. Jiang Y, Zhang X, Tang T, Zhou T, Shi G. Determination of endocrine disruptors in environmental water by single-drop microextraction and high-performance liquid chromatography. Analytical Letters. 2014;48(4):710–25.
72. Dos Anjos JP, de Andrade JB. Simultaneous determination of pesticide multiresidues in white wine and rosé wine by SDME/GC-MS. Microchemical Journal.2015;120:69–76.
73. Kaykhaii M, Abdi A. Rapid and sensitive determination of acrylamide in potato crisps using reversed-phase direct immersion single drop microextraction-gas chromatography. Analytical Methods.2013;5(5):1289.
74. George MJ, Marjanovic L. Rapid detection of atrazine and metolachlor in farm soils: gas chromatography − mass spectrometry – based analysis using the bubble-in-drop single drop microextraction enrichment method. Journal of Agricultural and Food Chemistry. 2014;62:7676–81.
75. Liu D, Min S. Rapid analysis of organochlorine and pyrethroid pesticides in tea samples by directly suspended droplet microextraction using a gas chromatography-electron capture detector. Journal of Chromatography A. 2012;1235:166–73.
76. [Internet]. Available from: