SavedAdd your journal

Journals / Turkish Journal of Analytical Chemistry / 2026 / Cilt: 8 Sayı: 3

Deep eutectic solvent-based dispersive liquid–liquid microextraction: Principles, developments, and applications in trace analysis

Derin Ötektik Çözücü Tabanlı Dispersif Sıvı–Sıvı Mikroekstraksiyon: İlkeler, Gelişmeler ve İz Analizindeki Uygulamalar

Yasemin Çağlar(GIRESUN UNIVERSITY)0000-0002-8437-5373
Pages
264–275
Publication Date
2026-09-30
🏛️Bibliographic metadata and full text access for this article are provided via DergiPark.
DergiPark Record ↗
✨

AI Summary & Key Takeaways

AI Insight
⚡ TL;DR(Too Long; Didn't Read)

In addition, the types of sample matrices investigated and the analytical performance characteristics are presented in a general framework.

📌 3 Key Takeaways

🎯
Objective & Hypothesis:Sample preparation remains one of the most critical and time-consuming steps in chemical analysis, particularly for the determination of trace-level analytes in complex matrices.
📊
Key Findings & Data:Methodological variations, including in-situ solvent formation, hybrid extraction techniques, and different dispersion strategies, are outlined.
💡
Conclusion & Impact:In addition, the types of sample matrices investigated and the analytical performance characteristics are presented in a general framework.
🔬Design:Review & Systematic Survey
📍Scope:Comprehensive Sample
⚙️Variables:Dispersif sıvı–sıvı mikroekstraksiyon · Yeşil analitik kimya · Derin ötektik çözücüler

Abstract

Sample preparation remains one of the most critical and time-consuming steps in chemical analysis, particularly for the determination of trace-level analytes in complex matrices. Conventional extraction techniques, such as liquid–liquid extraction and solid-phase extraction, are often associated with high solvent consumption, limited selectivity, and environmental concerns. In this context, dispersive liquid–liquid microextraction (DLLME) has emerged as an efficient miniaturized technique due to its rapid extraction kinetics, low solvent usage, and high enrichment capability. However, the widespread use of toxic organic solvents in classical DLLME systems restricts its sustainability and broader applicability. To address these limitations, recent research has focused on the development of greener extraction media, particularly deep eutectic solvents (DESs), which offer tunable physicochemical properties, low volatility, and improved compatibility with green analytical chemistry principles. These alternative solvents have enabled the design of more sustainable, efficient, and selective DLLME systems. This review, after addressing the fundamental extraction mechanism of DES-based DLLME, provides an overview of approaches developed for the determination of pesticides and heavy metals, with a primary focus on the chronological development of the reported methods. The studies are summarized in terms of physicochemical properties, the types of DESs used and their component ratios, as well as their analytical applications. Methodological variations, including in-situ solvent formation, hybrid extraction techniques, and different dispersion strategies, are outlined. In addition, the types of sample matrices investigated and the analytical performance characteristics are presented in a general framework.

Özet

Numune hazırlama, özellikle karmaşık matrislerde iz düzeydeki analitlerin tayini söz konusu olduğunda, kimyasal analizde en kritik ve zaman alıcı adımlardan biri olmaya devam etmektedir. Sıvı–sıvı ekstraksiyonu ve katı faz ekstraksiyonu gibi geleneksel ekstraksiyon teknikleri genellikle yüksek çözücü tüketimi, sınırlı seçicilik ve çevresel kaygılarla ilişkilendirilmektedir. Bu bağlamda, dispersif sıvı–sıvı mikroekstraksiyon (DLLME), hızlı ekstraksiyon kinetiği, düşük çözücü kullanımı ve yüksek zenginleştirme kapasitesi sayesinde etkin bir minyatürleştirilmiş teknik olarak öne çıkmıştır. Bununla birlikte, klasik DLLME sistemlerinde toksik organik çözücülerin yaygın kullanımı, yöntemin sürdürülebilirliğini ve daha geniş uygulama alanlarını sınırlamaktadır. Bu sınırlamaların üstesinden gelmek amacıyla, son yıllarda özellikle ayarlanabilir fizikokimyasal özellikler, düşük uçuculuk ve yeşil analitik kimya ilkeleriyle daha iyi uyumluluk sunan derin ötektik çözücüler (DES’ler) gibi daha çevre dostu ekstraksiyon ortamlarının geliştirilmesine odaklanılmıştır. Bu alternatif çözücüler, daha sürdürülebilir, verimli ve seçici DLLME sistemlerinin tasarlanmasına olanak sağlamıştır. Bu derleme, DES-temelli DLLME’nin temel ekstraksiyon mekanizmasını ele aldıktan sonra, pestisitler ve ağır metallerin tayini için geliştirilen yaklaşımlara genel bir bakış sunmakta olup, ağırlıklı olarak bildirilen yöntemlerin kronolojik gelişimine odaklanmaktadır. Çalışmalar, fizikokimyasal özellikler, kullanılan DES türleri ve bunların bileşen oranları ile analitik uygulamalar açısından özetlenmiştir. Yerinde çözücü oluşumu, hibrit ekstraksiyon teknikleri ve farklı dispersiyon stratejileri gibi yöntemsel varyasyonlar ana hatlarıyla ele alınmıştır. Ayrıca, incelenen numune matrisleri ve analitik performans özellikleri genel bir çerçevede sunulmuştur.

🔖

Cite This Article

Çağlar, Y. (2026). Deep eutectic solvent-based dispersive liquid–liquid microextraction: Principles, developments, and applications in trace analysis. Turkish Journal of Analytical Chemistry, Cilt: 8 Sayı: 3, 264–275. https://doi.org/10.51435/turkjac.1956533

📄 Full Text PDF Viewer

📄

PDF görüntüleyici hazırlanıyor...

References (68)

  1. A. Chisvert, S. Cárdenas, R. Lucena, Dispersive Micro-Solid Phase Extraction, TrAC Trends Anal Chem, 112, 2019, 226–233.
  2. M. Kabeer, Y. Hakami, M. Asif, T. Alrefaei, M. Sajid, Modern Solutions in Magnetic Analytical Extractions of Metals: A Review, TrAC Trends Anal Chem, 130, 2020, 115987.
  3. M. Sajid, M. Khaled Nazal, M. Rutkowska, N. Szczepańska, J. Namieśnik, J. Płotka-Wasylka, Solid Phase Microextraction: Apparatus, Sorbent Materials, and Application, Crit Rev Anal Chem, 49, 2019, 271–288.
  4. H. Pereira Neves, G. Max Dias Ferreira, G. Max Dias Ferreira, L. Rodrigues de Lemos, G. Dias Rodrigues, V. Albis Leão, A. Barbosa Mageste, Liquid-Liquid Extraction of Rare Earth Elements Using Systems That Are More Environmentally Friendly: Advances, Challenges and Perspectives, Sep Purif Technol, 282, 2022, 120064.
  5. Z. Mbanjwa, Method Development for Analysis of Non-Steroid Anti-Inflammatory Drugs (Nsaids) in Various Water Systems, Yüksek Lisans Tezi, University of Johannesburg, Faculty of Science, 2017.
  6. J. Płotka-Wasylka, K. Owczarek, J. Namieśnik, Modern Solutions in the Field of Microextraction Using Liquid as a Medium of Extraction, TrAC Trends Anal Chem, 85, 2016, 46–64.
  7. J. Płotka-Wasylka, N. Szczepańska, M. de la Guardia, J. Namieśnik, Miniaturized Solid-Phase Extraction Techniques, TrAC Trends Anal Chem, 73, 2015, 19–38.
  8. M.A. Jeannot, F.F. Cantwell, Solvent Microextraction into a Single Drop, Anal Chem, 68, 1996, 2236-2240.
  9. C.L. Arthur, J. Pawliszyn, Solid Phase Microextraction with Thermal Desorption Using Fused Silica Optical Fibers, Anal Chem, 62, 1990, 2145-2148.
  10. F. Pena-Pereira, C. Bendicho, D.M. Pavlović, A. Martín-Esteban, M. Díaz-Álvarez, Y. Pan, J. Cooper, Z. Yang, I. Safarik, K. Pospiskova, M.A. Segundo, E. Psillakis, Miniaturized Analytical Methods for Determination of Environmental Contaminants of Emerging Concern – A Review, Anal Chim Acta, 1158, 2021, 238108.
  11. J. Soares da Silva Burato, D.A. Vargas Medina, A.L. de Toffoli, E. Vasconcelos Soares Maciel, F. Mauro Lanças, Recent Advances and Trends in Miniaturized Sample Preparation Techniques, J Sep Sci, 43, 2020, 202–225.
  12. M. Rezaee, Y. Assadi, M.R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, Determination of Organic Compounds in Water Using Dispersive Liquid-Liquid Microextraction, J Chromatogr A, 1116, 2006, 1–9.
  13. M.A. Farajzadeh, M. Bahram, B.G. Mehr, J.Å. Jönsson, Optimization of Dispersive Liquid-Liquid Microextraction of Copper (II) by Atomic Absorption Spectrometry as Its Oxinate Chelate: Application to Determination of Copper in Different Water Samples, Talanta, 75, 2008, 832–840.
  14. M. Hossien-poor-Zaryabi, M. Chamsaz, T. Heidari, M.A.H. Zavar, M. Behbahani, M. Salarian, Application of Dispersive Liquid-Liquid Micro-Extraction Using Mean Centering of Ratio Spectra Method for Trace Determination of Mercury in Food and Environmental Samples, Food Anal Methods, 7, 2014, 352–359.
  15. H. Sereshti, M. Karimi, S. Samadi, Application of Response Surface Method for Optimization of Dispersive Liquid-Liquid Microextraction of Water-Soluble Components of Rosa Damascena Mill. Essential Oil, J Chromatogr A, 1216, 2009, 198–204.
  16. M. Karimi, H. Sereshti, S. Samadi, H. Parastar, Optimization of Dispersive Liquid-Liquid Microextraction and Improvement of Detection Limit of Methyl Tert-Butyl Ether in Water with the Aid of Chemometrics, J Chromatogr A, 1217, 2010, 7017–7023.
  17. A. Zgoła-Grześkowiak, T. Grześkowiak, Dispersive Liquid-Liquid Microextraction, TrAC Trends Anal Chem, 30, 2011, 1382–1399.
  18. P. Makoś, E. Słupek, J. Gębicki, Hydrophobic Deep Eutectic Solvents in Microextraction Techniques–A Review, Microchem J, 152, 2020.
  19. H. Yan, H. Wang, Recent Development and Applications of Dispersive Liquid-Liquid Microextraction, J Chromatogr A, 1295, 2013, 1–15.
  20. S.G. Dmitrienko, V.V. Apyari, V.V. Tolmacheva, M.V. Gorbunova, Dispersive Liquid–Liquid Microextraction of Organic Compounds: An Overview of Reviews, J Anal Chem, 75, 2020, 1237–1251.
  21. M. Sajid, Dispersive Liquid-Liquid Microextraction: Evolution in Design, Application Areas, and Green Aspects, TrAC Trends Anal Chem, 152, 2022.
  22. M. Sajid, Magnetic Ionic Liquids in Analytical Sample Preparation: A Literature Review, TrAC Trends Anal Chem, 113, 2019, 210–223.
  23. Á.I. López-Lorente, F. Pena-Pereira, S. Pedersen-Bjergaard, V.G. Zuin, S.A. Ozkan, E. Psillakis, The Ten Principles of Green Sample Preparation, TrAC Trends Anal Chem, 148, 2022, 116530.
  24. X.H. Zang, Q.H. Wu, M.Y. Zhang, G.H. Xi, Z. Wang, Developments of Dispersive Liquid-Liquid Microextraction Technique, Chin J Anal Chem, 37, 2009, 161–168.
  25. J. Grau, C. Azorín, J.L. Benedé, A. Chisvert, A. Salvador, Use of Green Alternative Solvents in Dispersive Liquid-Liquid Microextraction: A Review, J Sep Sci, 45, 2022, 210–222.
  26. W. Lu, S. Liu, Z. Wu, Recent Application of Deep Eutectic Solvents as Green Solvent in Dispersive Liquid–Liquid Microextraction of Trace Level Chemical Contaminants in Food and Water, Crit Rev Anal Chem, 52, 2022, 504–518.
  27. Q. Zhou, H. Bai, G. Xie, J. Xiao, Temperature-Controlled Ionic Liquid Dispersive Liquid Phase Micro-Extraction, J Chromatogr A, 1177, 2008, 43–49.
  28. M.A. Farajzadeh, M.R. Afshar Mogaddam, M. Aghanassab, Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction, Anal Methods, 8, 2016, 2576–2583.
  29. S. Jafarvand, F. Shemirani, Supramolecular-Based Dispersive Liquid-Liquid Microextraction: A Novel Sample Preparation Technique for Determination of Inorganic Species, Microchim Acta, 173, 2011, 353–359.
  30. Y. Cui, C. Li, J. Yin, S. Li, Y. Jia, M. Bao, Design, Synthesis and Properties of Acidic Deep Eutectic Solvents Based on Choline Chloride, J Mol Liq, 236, 2017, 338–343.
  31. A.P. Abbott, G. Capper, D.L. Davies, H.L. Munro, R.K. Rasheed, V. Tambyrajah, Preparation of Novel, Moisture-Stable, Lewis-Acidic Ionic Liquids Containing Quaternary Ammonium Salts with Functional Side Chains, Chem Commun, 2001, 1, 2010–2011.
  32. A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah, Novel Solvent Properties of Choline Chloride/Urea Mixtures, Chem Commun, 2003, 7, 70–71.
  33. E.L. Smith, A.P. Abbott, K.S. Ryder, Deep Eutectic Solvents (DESs) and Their Applications, Chem Rev, 114, 2014, 11060–11082.
  34. A. Shishov, A. Bulatov, M. Locatelli, S. Carradori, V. Andruch, Application of Deep Eutectic Solvents in Analytical Chemistry. A Review, Microchem J, 135, 2017, 33–38.
  35. M. Cvjetko Bubalo, N. Ćurko, M. Tomašević, K. Kovačević Ganić, I. Radojcic Redovnikovic, Green Extraction of Grape Skin Phenolics by Using Deep Eutectic Solvents, Food Chem, 200, 2016, 159–166.
  36. S. Khandelwal, Y.K. Tailor, M. Kumar, Deep Eutectic Solvents (DESs) as Eco-Friendly and Sustainable Solvent/Catalyst Systems in Organic Transformations, J Mol Liq, 215, 2016, 345–386.
  37. G. Li, K.H. Row, Utilization of Deep Eutectic Solvents in Dispersive Liquid-Liquid Micro-Extraction, TrAC Trends Anal Chem, 120, 2019, 115651.
  38. T. Zhekenov, N. Toksanbayev, Z. Kazakbayeva, D. Shah, F.S. Mjalli, Formation of Type III Deep Eutectic Solvents and Effect of Water on Their Intermolecular Interactions, Fluid Phase Equilib, 441, 2017, 43–48.
  39. F. Chemat, H. Anjum, A.M. Shariff, P. Kumar, T. Murugesan, Thermal and Physical Properties of (Choline Chloride + Urea + l-Arginine) Deep Eutectic Solvents, J Mol Liq, 218, 2016, 301–308.
  40. A.P. Abbott, G. Capper, K.J. McKenzie, K.S. Ryder, Electrodeposition of Zinc-Tin Alloys from Deep Eutectic Solvents Based on Choline Chloride, J Electroanal Chem, 599, 2007, 288–294.
  41. L.I.N. Tomé, V. Baião, W. da Silva, C.M.A. Brett, Deep Eutectic Solvents for the Production and Application of New Materials, Appl Mater Today, 10, 2018, 30–50.
  42. M.J. Gidado, A.A.N. Gunny, I.M. AlNashef, Deep Eutectic Solvents as Green Alternatives in Postharvest Fruit Preservation: A Comprehensive Review, Food Bioproc Tech, 18, 2025, 9109–9141.
  43. P. Makoś, E. Słupek, J. Gębicki, Hydrophobic Deep Eutectic Solvents in Microextraction Techniques–A Review, Microchem J, 152, 2020, 104384.
  44. Y. Shi, X. Li, Y. Shang, T. Li, K. Zhang, J. Fan, Effective Extraction of Fluorescent Brightener 52 from Foods by in Situ Formation of Hydrophobic Deep Eutectic Solvent, Food Chem, 311, 2020, 125870.
  45. A. Shishov, P. Terno, L. Moskvin, A. Bulatov, In-Syringe Dispersive Liquid-Liquid Microextraction Using Deep Eutectic Solvent as Disperser: Determination of Chromium (VI) in Beverages, Talanta, 206, 2020, 120209.
  46. Y. Shi, D. Xiong, Y. Zhao, T. Li, K. Zhang, J. Fan, Highly Efficient Extraction/Separation of Cr (VI) by a New Family of Hydrophobic Deep Eutectic Solvents, Chemosphere, 241, 2020, 125082.
  47. M.A. Farajzadeh, M. Sattari Dabbagh, A. Yadeghari, Deep Eutectic Solvent Based Gas-Assisted Dispersive Liquid-Phase Microextraction Combined with Gas Chromatography and Flame Ionization Detection for the Determination of Some Pesticide Residues in Fruit and Vegetable Samples, J Sep Sci, 40, 2017, 2252–2260.
  48. H. Zeng, K. Qiao, X. Li, M. Yang, S. Zhang, R. Lu, J. Li, H. Gao, W. Zhou, Dispersive Liquid–Liquid Microextraction Based on the Solidification of Deep Eutectic Solvent for the Determination of Benzoylureas in Environmental Water Samples, J Sep Sci, 40, 2017, 4563–4570.
  49. A. Bazmandegan-Shamili, S. Dadfarnia, A.M.H. Shabani, M.R. Moghadam, M. Saeidi, Temperature-Controlled Liquid–Liquid Microextraction Combined with High-Performance Liquid Chromatography for the Simultaneous Determination of Diazinon and Fenitrothion in Water and Fruit Juice Samples, J Sep Sci, 41, 2018, 2411-2418.
  50. M. Torbati, M.A. Farajzadeh, M.R. Afshar Mogaddam, M. Torbati, Development of Microwave-Assisted Liquid-Liquid Extraction Combined with Lighter than Water in Syringe Dispersive Liquid-Liquid Microextraction Using Deep Eutectic Solvents: Application in Extraction of Some Herbicides from Wheat, Microchem J, 147, 2019, 1103–1108.
  51. H. Heidari, S. Ghanbari-Rad, E. Habibi, Optimization Deep Eutectic Solvent-Based Ultrasound-Assisted Liquid-Liquid Microextraction by Using the Desirability Function Approach for Extraction and Preconcentration of Organophosphorus Pesticides from Fruit Juice Samples, J Food Compos Anal, 87, 2020, 103389.
  52. R. Kachangoon, J. Vichapong, Y. Santaladchaiyakit, R. Burakham, S. Srijaranai, An Eco-Friendly Hydrophobic Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction for the Determination of Neonicotinoid Insecticide Residues in Water, Soil and Egg Yolk Samples, Molecules, 25, 2020, 2785.
  53. B. Tesfaye, A. Gure, T.G. Asere, G.J. Molole, Deep Eutectic Solvent-Based Dispersive Liquid–Liquid Microextraction for Determination of Organochlorine Pesticides in Water and Apple Juice Samples, Microchem J, 195, 2023, 109428.
  54. M.V. Sengane, M. Sihlahla, P.N. Nomngongo, N. Mketo, Application of Deep Eutectic Solvent Based Dispersive Liquid–Liquid Microextraction Method Followed by HPLC-DAD for Quantification of Selected Neonicotinoid Pesticides in Vegetable Oils, Microchem J, 207, 2024, 111984.
  55. A. Hristozova, L. Vidal, M.Á. Aguirre, K. Simitchiev, A. Canals, Natural Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction of Pesticides in Drinking Waters Combined with GC-MS/MS Detection, Talanta, 282, 2025, 126967.
  56. L. Carbonell-Rozas, R. Canales, F.J. Lara, A.M. García-Campaña, M.F. Silva, A Natural Deep Eutectic Solvent as a Novel Dispersive Solvent in Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Droplet for the Determination of Pesticide Residues, Anal Bioanal Chem, 413, 2021, 6413–6424.
  57. A. Abasalizadeh, S.M. Sorouraddin, M.A. Farajzadeh, M.R. Afshar Mogaddam, Development of a Green Approach Based on DµSPE Combined with Deep Eutectic Solvent-Based DLLME for the Extraction of Some Pesticides from Vegetable Samples Prior to GC–FID and GC–MS, J Iran Chem Soc, 19, 2022, 4699-4707.
  58. A.H. Panhwar, M. Tuzen, T.G. Kazi, Ultrasonic Assisted Dispersive Liquid-Liquid Microextraction Method Based on Deep Eutectic Solvent for Speciation, Preconcentration and Determination of Selenium Species (IV) and (VI) in Water and Food Samples, Talanta, 175, 2017, 352–358.
  59. Ç. Arpa, S. Albayati, M. Yahya, Effervescence-Assisted Dispersive Liquid-Liquid Microextraction Based on Deep Eutectic Solvent for Preconcentration and FAAS Determination of Copper in Aqueous Samples, Int J Environ Anal Chem, 98, 2018, 938–953.
  60. A.S. Rad, R. Rahnama, M. Zakeri, M.R. Jamali, Dispersive Liquid–Liquid Microextraction Based on Green Type Solvents—“deep Eutectic Solvents”—for Highly Selective Separation and Efficient Preconcentration of Nickel in Water Samples, J Iran Chem Soc, 16, 2019, 1715–1722.
  61. M. Pourmohammad, M. Faraji, S. Jafarinejad, Extraction of Chromium (VI) in Water Samples by Dispersive Liquid–Liquid Microextraction Based on Deep Eutectic Solvent and Determination by UV–Vis Spectrophotometry, Int J Environ Anal Chem, 100, 2020, 1146–1159.
  62. E. Ragheb, M. Shamsipur, F. Jalali, M. Sadeghi, N. Babajani, N. Mafakheri, Magnetic Solid-Phase Extraction Using Metal–Organic Framework-Based Biosorbent Followed by Ligandless Deep-Eutectic Solvent-Ultrasounds-Assisted Dispersive Liquid–Liquid Microextraction (DES-USA-DLLME) for Preconcentration of Mercury (II), Microchem J, 166, 2021, 106209.
  63. B. Al Sayeda, F. Shah, N. Ullah, R.A. Khan, B. Ismail, A.M. Khan, J. Nisar, Hydrophobic Deep Eutectic Solvent-Based Dispersive Liquid–Liquid Microextraction for the Zinc Determination in Aqueous Samples: Multivariate Study, Int J Environ Sci Technol, 19, 2022, 8933–8944.
  64. I. Nemati, M. Faraji, S. Jafarinejad, M. Shirani, Development of a Deep Eutectic Solvent-Based Dispersive Liquid–Liquid Microextraction Coupled with Spectrophotometer Technique for Determination of Trace Amount of Hg(II) in Water Samples, Chem Pap, 77, 2023, 909–919.
  65. N. Mafakheri, M. Shamsipur, N. Babajani, Development of a Dispersive Liquid–Liquid Microextraction Procedure Based on a Natural Deep Eutectic Solvent for Ligand-Less Preconcentration and Determination of Heavy Metals from Water and Food Samples, Microchem J, 199, 2024, 110010.
  66. G.A. Shifera, T.T. Beyene, J. Kochito, A. Gure, In-Situ Formation of Deep Eutectic Solvent Based Dispersive Liquid-Liquid Microextraction for the Extraction of Cr(VI) from Water Samples before Its Determination by UV-Vis Spectrophotometry, Chin J Anal Chem, 54, 2026, 100685.
  67. T.A. Jouybari, H.A. Jouybari, F. Hosseini, M. Nesari, N. Fattahi, Evaluation of Blood Lead Levels in Opium Addicts and Healthy Control Group Using Novel Deep Eutectic Solvent Based Dispersive Liquid–Liquid Microextraction Followed by GFAAS, Environ Sci Pollut Res, 30, 2023, 24553–24561.
  68. A.J. Hadad, S.S. Affat, Deep Eutectic Solvents-Based Ultrasonic Assisted Dispersive Liquid-Liquid Microextraction with Using Nanoparticles for Determination of Cadmium and Lead in Real Samples, Cent Asian J Theor Appl Sci, 05, 2024, 604–621.