M. Abdel-rehim, M. Anderson, E. Portelius, C. Norsten-hoog, and L. G. Blomber, Determination of ropivacaine and its metabolites in human plasma using solid phase microextraction and GC-NPD / GC-MS', Journal of Microcolumn Separations, vol.13, issue.8, pp.313-321, 2001.

M. H. Abraham and A. F. Danil-de-namor, Solubility of electrolytes in 1,2-dichloroethane and 1,1-dichloroethane, and derived from free energies of transfer, Journal of Chemical Society, Faraday Transactions, vol.1, pp.952-96, 1974.

S. Aburuz, J. Millership, and J. Mcelnay, Determination of metformin in plasma using a new ion pair solid phase extraction technique and ion pair liquid chromatography, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 2003.

M. Aider, D. De-halleux, and L. Bazinet, Potential of continuous electrophoresis without and with porous membranes (CEPM) in the bio-food industry: review', Trends in Food Science and Technology, vol.19, pp.351-362, 2008.

W. J. Albery, J. F. Burke, E. B. Leffler, and J. Hadgraf, Interfacial Transfer Studied with a Rotating Diffusion Cell, Journal of Chemical Society Faraday Transactions, vol.1, pp.1618-1626, 1976.

W. J. Albery, A. M. Couper, J. Hadgraft, and C. Ryan, Journal of Chemical Society Faraday Transactions, vol.1, p.1124, 1974.

I. Ali, I. Hussain, M. M. Sanagi, W. A. Ibrahim, and H. Y. Aboul-enein, Analyses of biguanides and related compounds in biological and environmental samples by HPLC, Journal of Liquid Chromatography and Related Technologies, vol.38, issue.3, pp.303-321, 2015.

M. D. Alpendurada, Solid-phase microextraction: a promising technique for sample preparation in environmental analysis, Journal of Chromatography A, vol.889, pp.3-14, 2000.

A. Alshishani, A. Makahleh, H. F. Yap, E. A. Gubartallah, S. M. Salhimi et al., Ion-pair vortex assisted liquid-liquid microextraction with back extraction coupled with high performance liquid chromatography-UV for the determination of metformin in plasma, Talanta, vol.161, pp.398-404, 2016.

A. Alshishani, S. M. Salhimi, and B. Saad, Salting-out assisted liquid-liquid extraction coupled with hydrophilic interaction chromatography for the determination of biguanides in biological and environmental samples, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, pp.51-59, 2017.

A. Alshishani, M. Saaid, C. Basheer, and B. Saad, High performance liquid chromatographic determination of triclosan, triclocarban and methyl-triclosan in wastewater using mini-bar micro-solid phase extraction, Microchemical Journal, vol.147, pp.339-348, 2019.

A. Andrade-eiroa, M. Canle, V. Leroy-cancellieri, and V. Cerda, Solid-phase extraction of organic compounds: A critical review (Part I)', TrAC -Trends in Analytical Chemistry, vol.80, pp.641-654, 2016.

M. V. Appleyard, K. E. Murray, P. J. Coates, S. Wullschleger, S. E. Bray et al., Phenformin as prophylaxis and therapy in breast cancer xenografts, British Journal of Cancer, vol.106, issue.6, pp.1117-1128, 2012.

D. W. Arrigan, Bioanalytical Detection Based on Electrochemistry at Interfaces between Immiscible Liquids, Analyical Letter, vol.41, pp.3233-3252, 2008.

A. J. Bard, L. R. Faulkner, C. Wiley-basheer, A. Ali-alnedhary, B. S. Rao et al., Development and application of porous membrane-protected carbon nanotube microsolid-phase extraction combined with gas chromatography/mass spectrometry, Electrochemical Methods: Fundamentals and Applications, 2 nd Edition, vol.78, pp.2853-2858, 2001.

C. Basheer and H. K. Lee, Hollow fiber membrane-protected solid-phase microextraction of triazine herbicides in bovine milk and sewage sludge samples, J. Chromatogr. A, vol.1047, pp.189-194, 2004.

G. M. Ben-hander, Hollow fiber liquid phase microextraction with in situ derivatization for the determination of trace amounts of metformin hydrochloride (anti-diabetic drug) in biological fluids, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 2013.

G. M. Ben-hander, A. Makahleh, B. Saad, M. I. Saleh, and K. W. Cheng, Sequential hollow-fiber liquid phase microextraction for the determination of rosiglitazone and metformin hydrochloride (anti-diabetic drugs) in biological fluids, Talanta, 2015.

A. Berduque, A. Sherburn, M. Ghita, R. A. Dryfe, and D. M. Arrigan, Electrochemically modulated liquid-liquid extraction of ions, Analytical Chemistry, vol.77, issue.22, pp.7310-7318, 2005.

A. Berduque, Electrochemistry of Non-Redox-Active Poly ( propylenimine ) and Poly ( amidoamine ) Dendrimers at Liquid -Liquid Interfaces, pp.7356-7364, 2007.

A. Berduque and D. W. Arrigan, Selectivity in the coextraction of cation and anion by electrochemically modulated liquid-liquid extraction, Analytical Chemistry, vol.78, issue.8, pp.2717-2725, 2006.

E. Carasek, L. Morés, and J. Merib, Trends in Environmental Analytical Chemistry Basic principles , recent trends and future directions of microextraction techniques for the analysis of aqueous environmental samples, Biochemical Pharmacology, vol.19, p.60, 2018.

N. Casado, S. Morante-zarcero, D. Perez-quintanilla, and I. Sierra, Application of a hybrid ordered mesoporous silica as sorbent for solid-phase multi-residue extraction of veterinary drugs in meat by ultra-high-performance liquid chromatography coupled to ion-trap tandem mass spectrometry, Journal of Chromatography A, pp.24-37, 1459.

B. G. Charles, N. W. Jacobsen, and P. J. Ravenscroft, Rapid liquidchromatographic determination of metformin in plasma and urine, Clinical Chemistry, 1981.

C. Chen, Effects of Adjunctive Metformin on Metabolic Traits in Nondiabetic Clozapine-treated Patientswith Schizophrenia and the Effect of Metformin Discontinuation on Body Weight: A 24-week, Randomized, Double-blind, Placebo-Controlled Study, Journal of Clinical Psychiatry, vol.74, pp.424-330, 2013.

A. Chisvert, S. Cárdenas, and R. Lucena, Dispersive micro-solid phase extraction, TrAC -Trends in Analytical Chemistry, vol.112, pp.226-233, 2019.

C. J. Collins and D. W. Arrigan, Ion-transfer voltammetric determination of the ?-blocker propranolol in a physiological matrix at silicon membrane-based liquid|liquid microinterface arrays, Analytical Chemistry, vol.81, issue.6, pp.2344-2349, 2009.

C. J. Collins, A. Berduque, and D. W. Arrigan, Electrochemically modulated liquid-liquid extraction of ionized drugs under physiological conditions, Analytical Chemistry, vol.80, issue.21, pp.8102-8108, 2008.

T. A. Davis, Handbook of Industrial Membrane Technology, p.482, 1990.

J. R. Dean, Diagnosis and classification of diabetes mellitus' (2010) Diabetes Care, 2009.

M. De-fátima-alpendurada, Solid-phase microextraction: A promising technique for sample preparation in environmental analysis, Journal of Chromatography A, vol.889, issue.1-2, pp.3-14, 2000.

A. Esrafili, Y. Yamini, M. Ghambarian, and B. Ebrahimpour, Automated preconcentration and analysis of organic compounds by on-line hollow fiber liquidphase microextraction-high performance liquid chromatography, Journal of Chromatography A, vol.1262, pp.27-33, 2012.

A. Esrafili, M. Baharfar, M. Tajik, Y. Yamini, and M. Ghambarian, Two-phase hollow fiber liquid-phase microextraction, TrAC -Trends in Analytical Chemistry, vol.108, pp.314-322, 2018.

W. Fan, M. He, L. You, X. Zhu, B. Chen et al., Water-compatible graphene oxide/molecularly imprinted polymer coated stir bar sorptive extraction of propranolol from urine samples followed by high performance liquid chromatographyultraviolet detection, Journal of Chromatography A, pp.1-9, 1443.

M. Farajzadeh and N. Nouri, Derivatization and microextraction methods for determination of organic compounds by gas chromatography, Trends in Analytical Chemistry, vol.55, pp.14-23, 2014.

S. Y. Feng, E. P. Lai, E. Dabek-zlotorzynska, and S. Sadeghi, Molecularly imprinted solid-phase extraction for the screening of antihyperglycemic biguanides, Journal of Chromatography A, vol.1027, issue.1-2, pp.155-160, 2004.

M. A. Fernandez, L. C. Andre, and Z. L. Cardeal, Hollow fibre liquid-phase microextraction-gas chromatography-mass spectrometry method to analyze bisphenol A and other plasticizer metabolites, Journal of Chroomatography A, vol.1481, pp.31-36, 2017.

R. Q. Gabr, R. S. Padwal, and D. R. Brocks, Determination of Metformin in Human Plasma and Urine by High-Performance Liquid Chromatography Using Small Sample Volume and Conventional Octadecyl Silane Column, vol.13, pp.486-494, 1995.

P. Ganesan, R. Kamaraj, G. Sozhan, and S. Vasuvedan, Oxidised multiwalled carbon nanotubes as adsorbent for the removal of manganese from aqueous solution, Environmental Science and Pollution Research, vol.20, pp.987-996, 2013.

A. Gaona-gómez and C. H. Cheng, Modification of zeolite L (LTL) morphology using diols, (OH) 2(CH 2) 2n+2O n (n = 0, 1, and 2)', Microporous and Mesoporous Materials, 153, pp.227-235, 2012.

C. Gavach, T. Mlodnicka, and . J. Guastalla, Proceedings of the academy of Sciences, vol.266, p.18, 1968.

D. Ge and H. K. Lee, Ionic liquid based dispersive liquid-liquid microextraction coupled with micro-solid phase extraction of antidepressant drugs from environmental water samples, Journal of Chromatography A, vol.1317, pp.217-222, 2013.

C. Georgi??, I. Sora, F. Albu, and C. M. Monciu, comparison of a lc/ms method with a lc/uv method for the determination of metformin in plasma samples, Farmacia, issue.2, p.58, 2010.

N. Gilart, New coatings for stir-bar sorptive extraction of polar emerging organic contaminants, TrAC -Trends in Analytical Chemistry, vol.54, pp.11-23, 2014.

V. Gobry, Generalization of ionic partition diagrams to lipophilic compounds and to biphasic systems with variable phase volume ratios, Electrochemistry Communications. Elsevier B.V, vol.123, issue.43, pp.137-139, 2001.

L. Guo and H. K. Lee, Development of multiwalled carbon nanotubes based micro-solid-phase extraction for the determination of trace levels of sixteen polycyclic aromatic hydrocarbons in environmental water samples, Journal of Chromatography A, vol.1218, pp.9321-9327, 2011.

Q. Han, Graphene as an efficient sorbent for the SPE of organochlorine pesticides in water samples coupled with GC-MS', Journal of Separation Science, vol.36, pp.3586-3591, 2013.

E. Haque, J. W. Jun, and S. H. Jhung, Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material, iron terephthalate (MOF-235), Journal of Hazardous Materials, vol.185, issue.1, pp.507-511, 2011.

J. G. Hardman, L. E. Limbird, A. G. Gilman, G. Herzog, S. Flynn et al., Electroanalytical behavior of poly-l-lysine dendrigrafts at the interface between two immiscible electrolyte solutions, Analytical Chemistry, 1996.

G. Herzog, Recent developments in electrochemistry at the interface between two immiscible electrolyte solutions for ion sensing, Analyst. Royal Society of Chemistry, vol.140, issue.12, pp.3888-3896, 2015.
URL : https://hal.archives-ouvertes.fr/hal-01505604

G. Herzog, V. Kam, and D. W. Arrigan, Electrochemical behaviour of haemoglobin at the liquid/liquid interface, Electrochimica Acta, vol.53, pp.7204-7209, 2008.

A. P. Hill and R. J. Young, Getting physical in drug discovery: A contemporary perspective on solubility and hydrophobicity, 2010.

, , vol.15, pp.648-655

L. Q. Hung, J. Electroanal. Chem, vol.115, pp.159-174, 1980.

K. M. Huttunen, Determination of metformin and its prodrugs in human and rat blood by hydrophilic interaction liquid chromatography, Journal of Pharmaceutical and Biomedical Analysis Journal of Pharmaceutical and Biomedical, vol.50, pp.469-474, 2009.

S. Ijima, Helical microtubules of graphitic carbon, Nature, vol.354, pp.56-58, 1991.

T. Iwata, H. Nagatani, and T. Osakai, Determination of the Electrostatic Potential of Oil-in-Water Emulsion Droplets by Combined Use of Two Membrane Potential-Sensitive Dyes, Analytical Sciences, vol.33, issue.7, pp.813-819, 2017.

R. Jain and R. Singh, Applications of dispersive liquid-liquid microextraction in forensic toxicology, TrAC Trends in Analytical Chemistry, vol.75, pp.227-237, 2016.

J. J. Juan, F. Fang, M. Ming, and Z. Z. Xing, Study on a new precolumn derivatization method in the determination of metformin hydrochloride, Journal of Chromatografic Sciences, vol.44, pp.193-199, 2006.

M. Karami, On-chip pulsed electromembrane extraction as a new concept for analysis of biological fluids in a small device, Journal of Chromatography A, vol.1527, pp.1-9, 2017.

S. Kanimozhi, C. Basheer, K. Narasimhan, L. Liu, S. Koh et al., Application of porous membrane protected micro-solid-phaseextraction combined with gas chromatography-mass spectrometry for the determination of estrogens in ovarian cyst fluid samples, Analytica Chimica Acta, 2011.

B. V. Elsevier, , vol.687, pp.56-60

H. Kataoka, H. L. Lord, and J. Pawliszyn, Applications of solid -phase microextraction in food analysis, Journal of Chromatography A, vol.880, pp.35-62, 2000.

T. Khezeli and A. Daneshfar, Development of dispersive micro-solid phase extraction based on micro and nano sorbents', TrAC -Trends in Analytical Chemistry, vol.89, pp.99-118, 2017.

B. Kimmel and S. E. Inzucchi, Oral Agents for Type 2 Diabetes: An Update', @bullet clinical diabetes, p.23, 2005.

J. M. Kokosa, Recent trends in using single-drop microextraction and related techniques in green analytical methods, Trends in Analytical Chemistry, vol.71, pp.194-204, 2015.

J. Koryta, Electrochemical polarization pehnomena at the interface of two immiscible electrolyte solutions. II Progress since 1978, Electrochimica Acta, vol.29, issue.4, pp.445-452, 1983.

J. Koryta, M. B?ezina, and . P. Vanýsek, Journal of Electroanalytical Chemistry, vol.75, p.211, 1977.

B. Kralj and R. A. Dryfe, Hydrodynamic voltammetry at the liquid/liquid interface: The rotating diffusion cell, Journal of Physical Chemistry B, vol.106, issue.26, pp.6732-6739, 2002.

B. Kralj and R. A. Dryfe, Hydrodynamic voltammetry at the liquid|liquid interface: Facilitated ion transfer and the rotating diffusion cell, Journal of Electroanalytical Chemistry, vol.560, issue.2, pp.127-133, 2003.

B. Kralj and R. A. Dryfe, The rotating paddle cell, Electrochemistry Communications, vol.5, issue.4, pp.325-328, 2003.

T. R. Krishnan and I. Ibraham, Solid-phase extraction technique for the analysis of biological samples, Journal of Pharmaceutical and Biomedical Analysis, pp.90001-90010, 1994.

E. P. Lai and S. Y. Feng, Solid phase extraction-Non-aqueous capillary electrophoresis for determination of metformin, phenformin and glyburide in human plasma, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, vol.843, issue.1, pp.94-99, 2006.

J. Langmaier, M. Pizl, Z. Samec, and S. Zalis, Extreme Basicity of Biguanide Drugs in Aqueous Solutions: Ion Transfer Voltammetry and DFT Calculations, Journal of Physical Chemistry A, 2016.

H. J. Lee, P. D. Beattie, B. J. Seddon, M. D. Osborne, and H. H. Girault, Amperometric ion sensors based on laser-patterned composite polymer membranes, Journal of Electroanalytical Chemistry, vol.440, issue.1-2, pp.73-82, 1997.

T. P. Lee, B. Saad, E. P. Ng, and B. Salleh, Zeolite Linde Type L as micro-solid phase extraction sorbent for the high performance liquid chromatography determination of ochratoxin A in coffee and cereal, Journal of Chromatography A, pp.46-54, 1237.

Y. Li, L. Li, and J. Yu, Applications of Zeolites in Sustainable Chemistry, pp.928-949, 2017.

A. Liu and S. P. Coleman, Determination of metformin in human plasma using hydrophilic interaction liquid chromatography-tandem mass spectrometry, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 2009.

S. Magiera, J. Hejniak, and J. Baranowski, Comparison of different sorbent materials for solid-phase extraction of selected drugs in human urine analyzed by UHPLC-UV', Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences. Elsevier B.V, vol.958, pp.22-28, 2014.

A. Makahleh, H. F. Yap, and B. Saad, Vortex-assisted liquid-liquid-liquid microextraction (VALLLME) technique: A new microextraction approach for direct liquid chromatography and capillary electrophoresis analysis, Talanta, vol.143, pp.394-401, 2015.

R. D. Mcdowall, J. C. Pearce, and G. S. Murkitt, Liquid-solid sample preparation in drug analysis, Journal of Pharmaceutical & Biomedical Analysis, vol.4, issue.1, pp.3-21, 1986.

M. P. Mousavi, S. Kashefolgheta, A. Stein, and P. Buhiman, Electrochemical stability of quaternary ammonium cations: An experimental and computational study, Journal of The electrochemical Society, vol.163, issue.2, pp.74-80, 2016.

W. M. Mullett, Determination of drugs in biological fluids by direct injection of samples for liquid-chromatographic analysis, Journal of Biochemical and Biophysical Methods, 2007.

N. N. Naing, S. F. Li, and H. K. Lee, Evaluation of graphene-based sorbent in the determination of polar environmental contaminants in water by micro-solid phase extraction-high performance liquid chromatography, Journal of Chromatography A. Elsevier B.V, pp.29-36, 1427.

N. N. Naing, S. F. Yau-li, and H. K. Lee, Magnetic micro-solid-phaseextraction of polycyclic aromatic hydrocarbons in water, Journal of Chromatography A. Elsevier B.V, pp.23-30, 1440.

A. Namera and T. Saito, Advances in monolithic materials for sample preparation in drug and pharmaceutical analysis, TrAC -Trends in Analytical Chemistry, vol.45, pp.182-196, 2013.

N. R. Neng, A. R. Silva, and J. M. Nogueira, Adsorptive microextraction techniques-Novel analytical tools for trace levels of polar solutes in aqueous media, Journal of Chromatography A. Elsevier B.V, vol.1217, issue.47, pp.7303-7310, 2010.

J. E. Nestler, Metformin for the Treatment of the Polycystic Ovary Syndrome, The New England Journal of Medicine, vol.358, pp.47-54, 2008.

J. M. Nogueira, Novel sorption-based methodologies for static microextraction analysis: A review on SBSE and related techniques, Analytica Chimica Acta. Elsevier B.V, vol.757, pp.1-10, 2012.

J. M. Nogueira, Stir-bar sorptive extraction: 15 years making sample preparation more environment-friendly, TrAC -Trends in Analytical Chemistry, 2015.

B. V. Elsevier, , vol.71, pp.214-223

L. Nováková and H. Vl?ková, A review of current trends and advances in modern bio-analytical methods: Chromatography and sample preparation, Analytica Chimica Acta, 2009.

M. Ohta, M. Iwasaki, M. Kai, and Y. Ohkura, Determintion of a biguanide, metformin, by high-performance liquid chromatography with precolumn fluoresence detector, Analytical Sciences, vol.9, pp.217-220, 1993.

A. J. Olaya, P. Ge, and H. H. Girault, Ion transfer across the water|trifluorotoluene interface, Electrochemistry Communications, vol.19, issue.1, pp.101-104, 2012.

N. S. Pano-farias, S. G. Ceballos-magana, R. Muniz-valencia, J. M. Jurado, A. Alcazar et al., Direct immersion single drop microextraction method for multi-class pesticides analysis in mango using GC-MS', Food Chemistry, vol.237, pp.30-38, 2017.

P. Partani, Y. Modhave, S. Gurule, A. Khuroo, and T. Monif, Simultaneous determination of propranolol and 4-hydroxy propranolol in human plasma by solid phase extraction and liquid chromatography/electrospray tandem mass spectrometry, Journal of Pharmaceutical and Biomedical Analysis, vol.50, pp.966-976, 2009.

D. M. Pavlovi?, S. Babic, A. J. Horvat, and M. Kastelan-macan, Sample preparation in analysis of pharmaceuticals, TrAC -Trends in Analytical Chemistry, vol.26, issue.11, pp.1062-1075, 2007.

J. Pawliszyn, J. Pawliszyn, and C. L. Arthur, Solid phase microextraction with thermal desorption using fused silica optical fibre, Analytical Chemistry, vol.62, issue.19, pp.2145-2148, 1990.

J. Pawliszyn and S. Pedersen-bjergaard, Analytical Microextraction: Current Status and Future Trends, Journal of Chromatographic Science, vol.44, issue.6, pp.291-307, 2006.

J. Pawliszyn and Z. Zhang, Headspace solid-phase microextraction, Analytical Chemistry, vol.65, pp.1843-1852, 1993.

S. Pedersen-bjergaard and K. E. Rasmussen, Electrical potential can drive liquid-liquid extraction for sample preparation in chromatography, TrAC -Trends in Analytical Chemistry, vol.27, issue.10, pp.934-941, 2008.

P. Peljo and H. H. Girault, Liquid/Liquid Interfaces, Electrochemistry at

J. Plotka-wasylka, N. Szczepanska, M. De-la-guardia, and J. Namiesnik, , 2015.

, Miniaturized solid-phase extraction techniques, TrAC -Trends in Analytical Chemistry, vol.73, pp.19-38

L. Poltorak, E. J. Sudhölter, and L. C. De-smet, Effect of charge of quartenary ammonium cations on lipophilicity and electroanalytical parameters: Task for ion transfer voltammetry', Journal of Electroanalytical Chemistry, vol.796, pp.66-74, 2017.

V. Porta, S. G. Schramm, E. K. Kano, E. E. Koono, Y. P. Armando et al., HPLC-UV determination of metformin in human plasma for application in pharmacokinetics and bioequivalence studies, Journal of Pharmaceutical and Biomedical Analysis, 2008.

M. R. Poujavid, M. Rabieh, S. R. Yousefi, M. R. Jamali, M. Rezaee et al., Study on column SPE with synthesized graphene oxide and FAAS for determination of trace amount of Co(II) and Ni(II) ions in real samples, Materials Science and Engineering C, vol.47, pp.114-122, 2015.

, Profiles of drugs substances, excipients and related methodology, vol.4325, 1975.

B. Quinn and K. Kontturi, Aspects of electron transfer at ITIES', Journal of Electroanalytical Chemistry, vol.483, pp.124-134, 2000.

M. A. Rahman and H. Doe, Ion transfer of tetraalkylammonium cations at an interface between frozen aqueous solution and 1,2-dichloroethane, Journal of Electroanalytical Chemistry, vol.424, pp.159-164, 1997.

F. Reymond, G. Steyaert, P. Carrupt, B. Testa, and H. Girault, Ionic partition diagrams: A potential-pH representation, Journal of the American Chemical Society, vol.118, issue.47, pp.11951-11957, 1996.

M. S. Ross, Determination of metformin in biological fluids by derivatization followed by high-performance liquid chromatography, Journal of Chromatography, vol.133, pp.408-411, 1977.

E. Santigosa, S. Maspoch, and M. Ramos-payán, Liquid phase microextraction integrated into a microchip device for the extraction of fluoroquinolones from urine samples, Microchemical Journal, pp.280-286, 2018.

Z. Samec, Electrochemistry at the interface between two immiscible electrolyte solutions, Pure Applied Chemistry, vol.76, issue.12, pp.2147-2180, 2004.

Z. Samec, A. Trojánek, J. Langmaier, and E. Samcová, Journal of Electroanalytical Chemistry, p.481, 2000.

M. Sajid, Porous membrane protected micro-solid-phase extraction: A review of features, advancements and applications, Analytica Chimica Acta, vol.965, pp.36-53, 2017.

. Sanchez, L. J. Vallejo, J. M. Ovejero, R. A. Fernandez, and S. A. Dassie, Simple Ion Transfer at Liquid|Liquid Interfaces, International Journal of Electrochemistry, pp.1-34, 2012.

M. Scanlon, Electrochemical processes of bio-analytical importance at micro-and nano-liquid | liquid interfaces, 2009.

M. D. Scanlon, E. Smirnov, T. J. Stockmann, and P. Peljo, Gold Nanofilms at Liquid-Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics, Chemical Reviews, vol.118, issue.7, pp.3722-3751, 2018.
URL : https://hal.archives-ouvertes.fr/hal-01974503

M. D. Scanlon, J. Strutwolf, and D. W. Arrigan, Voltammetric behaviour of biological macromolecules at arrays of aqueous|organogel micro-interfaces, Physical Chemistry Chemical Physics, vol.12, issue.34, pp.10040-10047, 2010.

M. Scheurer, F. Sacher, and H. Brauch, Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment, Water Research, vol.46, issue.15, pp.4790-4802, 2012.

M. Senda, T. Kakiuchi~, and T. Osakais, Electrochemistry at the interface between two immiscible electrolyte solutions, Elecrrochimica Acto, vol.36, issue.2, pp.253-262, 1991.

P. Sengupta, U. Bhaumik, A. Ghosh, A. K. Sarkar, B. Chatterjee et al., LC-MS-MS Development and Validation for Simultaneous Quantitation of Metformin, Glimepiride and Pioglitazone in Human Plasma and Its Application to a Bioequivalence Study, Chromatographia, vol.69, pp.1243-1250, 2009.

R. C. Sequeiros, N. R. Neng, F. C. Portugal, M. L. Pinto, J. Pires et al., Development and application of stir bar sorptive extraction with polyurethane foams for the determination of testosterone and methenolone in urine matrices, Journal of Chromatohgraphic Sciences, vol.49, pp.297-302, 2011.

P. A. Shah and P. S. Shrivastav, Ion-pair solid phase extraction for the simultaneous separation and quantitation of metformin and canagliflozin in human plasma by LC-MS/MS', Microchemical Journal, vol.143, pp.181-189, 2018.

L. Shi, J. Xie, and L. Du, Determination of phenformin hydrochloride employing a sensitive fluorescent probe, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol.162, pp.98-104, 2016.

A. K. Singh, E. R. Kedor-hackmann, and M. I. Santoro, Enantiomeric separation and quantitative determination of propranolol enantiomers in pharmaceutical preparations by chiral liquid chromatography, Revista Brasileira de Ciências Farmacêuticas Brazilian Journal of Pharmaceutical Sciences, issue.3, p.40, 2004.

R. Sitko, B. Zawisza, and E. Malicka, Graphene as a new sorbent in analytical chemistry, TrAC Trends in Analytical Chemistry, vol.5, pp.33-43, 2013.

L. K. Sørensen, Determination of metformin and other biguanides in forensic whole blood samples by hydrophilic interaction liquid chromatography-electrospray tandem mass spectrometry, Biomedical Chromatography, vol.26, issue.1, pp.1-5, 2012.

A. Spietelun, L. Marcinkowski, M. D. Guardia, and J. Namiesnik, Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry, Journal of Chromatography A, pp.1-13, 1321.

J. Sterne, Du nouveau dans les antidi-abetiques. La NN dimethylamine guanyl guanide, pp.1295-1296, 1957.

T. J. Stockmann, A. M. Montgomery, and Z. Ding, Determination of alkali metal ion transfers at liquid|liquid interfaces stabilized by a micropipette, Journal of Electroanalytical Chemistry, vol.684, pp.6-12, 2012.

J. Szulga, Introduction to random chaos, 1998.

F. Tache, V. David, A. Farca, and A. Medvedovici, HPLC-DAD determination of Metformin in human plasma using derivatization with p-nitrobenzoyl chloride in a biphasic system, Microchemical Journal, 2001.

K. Tahara, A. Yonemoto, Y. Yoshiyama, T. Nakamura, M. Aizawa et al., Determination of antihyperglycemic biguanides in serum and urine using a ion-pair solid-phase extraction technique followed by HPLC-UV on a pentafluorophenylpropyl column and on an octadecyl column, Biomedical Chromatography, vol.20, pp.1200-1205, 2006.

S. Tang, T. Qi, P. D. Ansah, J. C. Fouemina, W. Shen et al., Single-drop microextraction, TrAC -Trends in Analytical Chemistry, 2018.

H. L. Teo, L. Wong, Q. Liu, T. L. Teo, T. K. Lee et al., Simple and accurate measurement of carbamazepine in surface water by use of porous membraneprotected micro-solid-phase extraction coupled with isotope dilution mass spectrometry, Analytical Chimica Acta, vol.912, pp.49-57, 2016.

, The International Pharmacopoeia, 19th WHO Model List of Essential Medicines, pp.1-43, 2015.

A. Tiselius, Transaction of Faraday Society, vol.33, pp.524-531, 1973.

G. Tucker, Metformin kinetics in healthy subjects and in patients with diabetes mellitus, British Journal of Clinical Pharmacology, 1981.

S. M. Ulmeanu, H. Jensen, Z. Samec, G. Bouchard, P. A. Carrupt et al., Journal of Electroanalytical Chemistry, vol.530, issue.1-2, pp.10-15, 2002.

L. S. Vallejo, J. Ovejeri, R. Fernandez, and S. A. Dassie, Simple ion transfer at liquid|liquid interfaces, International Journal of Electrochemistry, pp.1-34, 2012.

P. Vanýsek, Analytical applications of electrified interfaces between two immiscible solutions, Trends in Analytical Chemistry, issue.93, p.87026, 1993.

I. Vasconcelos and C. Fernandes, Magnetic solid phase extraction for determination of drugs in biological matrices', TrAC -Trends in Analytical Chemistry, vol.89, pp.41-52, 2017.

M. Velázquez-manzanares, Fundamentals and Applications in Electrochemistry of Liquid-liquid Interfaces', Procedia Chemistry, vol.12, pp.100-107, 2014.

M. Velický, K. Y. Tam, and R. A. Dryfe, Hydrodynamic voltammetry at the liquid-liquid interface: Application to the transfer of ionised drug molecules, Journal of Electroanalytical Chemistry, vol.683, pp.94-102, 2012.

M. Velický, K. Y. Tam, and R. A. Dryfe, Permeation of a fully ionized species across a polarized supported liquid membrane, Analytical Chemistry, vol.84, issue.5, pp.2541-2547, 2012.

M. Velický, K. Y. Tam, and R. A. Dryfe, Mechanism of ion transfer in supported liquid membrane systems: Electrochemical control over membrane distribution, Analytical Chemistry, vol.86, issue.1, pp.435-442, 2014.

V. Vi?ka?kait? and A. Padarauskas, Ionic liquids in microextraction techniques, Central European Journal of Chemistry, vol.10, issue.3, pp.652-674, 2012.

A. G. Volkov and V. S. Markin, Chapter 4 Electric properties of oil/water interfaces, Interface Science and Technology, pp.80006-80007, 2004.

C. Vraka, L. Nics, K. Wagner, M. Hacker, W. Wadsak et al., LogP, a yesterday's value?', Nuclear Medicine and Biology, vol.50, pp.1-10, 2017.

T. Walle, U. K. Walle, and L. S. Olanoff, Quantitative account of propranolol metabolism in urine of normal man, Drug Metabolism and Disposition, vol.13, pp.204-209, 1985.

T. Wandlowski, V. Mare?ek, and Z. Samec, Galvani potential scales for waternitrobenzene andd water-1,2-dichloroethane interfaces, Electrochimica Acta, vol.35, issue.7, pp.1173-1175, 1990.

X. Wang, Y. Wang, Y. Qin, L. Ding, Y. Chen et al., Sensitive and selective determination of polycyclic aromatic hydrocarbons in mainstream cigarette smoke using a graphene-coated solid-phase microextraction fibre prior to GC/MS, Talanta, vol.140, pp.102-108, 2015.

A. Warade, R. Gaikwad, R. Sapkal, and V. Sapkal, Simulation of multistage countercurrent liquid-liquid extraction, Leonardo Journal of Sciences, pp.79-94, 2011.

X. Wu, B. Zhu, L. Lu, W. Huang, and D. Pang, Optimization of a solid phase extraction and hydrophilic interaction liquid chromatography-tandem mass spectrometry method for the determination of metformin in dietary supplements and herbal medicines', Food Chemistry, 2012.

X. Wu, H. Hong, X. Liu, W. Guan, L. Meng et al., Graphenedispersive solid-phase extraction of phthalate acid esters from environmental water', Science of the Total Environment, vol.444, pp.224-230, 2013.

J. Xiao, J. Wang, H. Fan, Q. Zhou, and X. Liu, Recent advances of adsorbents in solid phase extraction for environmental samples, International Journal of Environmental Analytical Chemistry. Taylor & Francis, vol.96, issue.5, pp.407-435, 2016.

T. Yamamoto, M. Kusama, K. Matsuno, E. Sugiyama, Y. Yamada et al., A new method for determination of buformin in plasma and urine by ion-paired reversed-phase HPLC with ultraviolet detection, Biomedical Chromatography, vol.16, issue.7, pp.453-454, 2002.

Y. Yamini, M. Rezazadeh, and S. Seidi, Liquid-phase microextraction -The different principles and configurations, TrAC -Trends in Analytical Chemistry, 2019.

, , vol.112, pp.264-272

X. Yang, C. Yang, and X. Yan, Zeolite imidazolate framework-8 as sorbent for on-line solid-phase extraction coupled with high-performance liquid chromatography for the determination of tetracyclines in water and milk samples, Journal of Chromatography A, vol.1304, pp.28-33, 2013.

J. Zhang, L. Ding, A. Wen, F. Wu, L. Sun et al., An HPLC-ESI-MS method for the determination of propranolol in human plasma and its application to pharmacokinetic studies, Asian Journal of Pharmaceutical Sciences, vol.4, issue.3, pp.169-177, 2009.

J. Zhang, Y. Wang, G. W. Stevens, and W. Fei, A state-of-the-art review on single drop study in liquid-liquid extraction: Experiments and simulations, Chinese Journal of Chemical Engineering, 2019.

L. Zhang, Y. Kitazumi, and T. Kakiuchi, Potential-dependent adsorption and transfer of poly(diallyldialkylammonium) ions at the nitrobenzene|water interface, Langmuir, vol.27, issue.21, pp.13037-13042, 2011.

J. Zhou, P. Zeng, J. B. Sun, F. Q. Wang, and Q. Zhang, Application of twophase hollow fiber liquid phase microextraction coupled with high-performance liquid chromatography for the study of the echinacoside pharmacokinetics in Parkinson's disease rat plasma, Journal of Pharmaceutical and Biomedical Analysis, pp.27-33, 2013.

A. ?wir-ferenc and M. Biziuk, Mechanism of Solid Phase Extraction Process', Department of Analytical Chemistry, Chemical Faculty, Gda?sk university of Technology, 15(Solid Phase Extraction Technique -Trends, Opportunities and Applications), pp.677-69, 2006.

, Calibration curves for graphene and zeolite Figure i. Calibration curves plotted for (a) graphene and (b) zeolite

, 182 V) et l'eau (Wandlowski et al, 1990), et [TMA + ]o et [TMA + ]w sont les concentrations de TMA + dans les phases organique et aqueuse

, Procédure d'extraction liquide-liquide à modulation électrochimique par gradient de concentration d'ion commun. Les cations cibles sont extraits de l'échantillon aqueux vers la phase organique avant d'être ré-extraits vers une phase aqueuse finale, et 3 correspondent aux étapes initiales, intermédiaires et finales auxquelles les phases aqueuses sont analysées par CLHP, vol.2

, La solution organique utilisée pour l'extraction contenait 10 mM de TMA + TPBCl -. Sur la base de ces concentrations de TMA + , la valeur initiale de ? ? était de +0,392 V, ce qui devrait être suffisant pour extraire 100 % des trois ions ciblés, sur une base thermodynamique. Toutefois, l'extraction est beaucoup plus faible que prévu : 27 % pour le MET, 44 % pour le PHEBI et 76 % pour le PHEN (Figure 4.3A). Lorsque la concentration initiale du médicament est réduite à 1,64 µM, l'efficacité d'extraction augmente à 84,2 % pour le MET, 100 % pour le PHEBI et 100 % pour le PHEN, Les chromatogrammes avant et après l'extraction sont présentés à la graphique 4.3 pour un ensemble donné de paramètres d'extraction. Le premier échantillon analysé contenait du MET, du PHEBI et du PHEN (164 µM chacun) et 1 µM de TMA +

, PHEBI et PHEN à (A) 164 µM chacun et à (B) 1,64 µM chacun avant (1) et après (2) extraction, en phase aqueuse de contreextraction (3). Les conditions d'extraction étaient les suivantes