Polycation-sensitive membrane electrode for determination of heparin based on controlled release of protamine.

A polycation-selective polymeric membrane electrode using dinonylnaphthalene sulfonate as an ion exchanger has been developed as a protamine controlled-release system for potentiometric detection of heparin. The incorporation of tetradodecylammonium tetrakis(4-chlorophenyl)borate as a lipophilic salt in the membrane dramatically improves the sensor's selectivity towards protamine over sodium ions via influencing the activity coefficient of protamine in the membrane, and a stable potential baseline can be obtained in the presence of an electrolyte background. The electrostatic binding interaction between heparin and protamine decreases the concentration of free protamine released at the sample-membrane interface and facilitates the stripping of protamine out of the membrane surface via the ion-exchange process with sodium ions, thus decreasing the membrane potential. Under optimal conditions, the proposed polymeric membrane electrode exhibits a linear relationship between the initial slope of the potential change and the heparin concentration in the range of 0.025-1.25 U mL(-1) with an improved detection limit of 0.01 U mL(-1).

[1]  W. Qin,et al.  Label-free and substrate-free potentiometric aptasensing using polycation-sensitive membrane electrodes. , 2012, Analytical chemistry.

[2]  Y. Kang,et al.  Highly sensitive potentiometric strip test for detecting high charge density impurities in heparin. , 2011, Analytical chemistry.

[3]  M. Meyerhoff,et al.  Reversible detection of heparin and other polyanions by pulsed chronopotentiometric polymer membrane electrode. , 2010, Analytical chemistry.

[4]  B. Liu,et al.  Naked-eye detection and quantification of heparin in serum with a cationic polythiophene. , 2010, Analytical chemistry.

[5]  W. Qin,et al.  Current-driven ion fluxes of polymeric membrane ion-selective electrode for potentiometric biosensing. , 2009, Journal of the American Chemical Society.

[6]  W. Qin,et al.  Potentiometric sensing of butyrylcholinesterase based on in situ generation and detection of substrates. , 2009, Chemical communications.

[7]  M. Meyerhoff,et al.  Detection of high-charge density polyanion contaminants in biomedical heparin preparations using potentiometric polyanion sensors. , 2008, Analytical chemistry.

[8]  E. Samcová,et al.  Counterion binding to protamine polyion at a polarised liquid–liquid interface , 2007 .

[9]  E. Samcová,et al.  Potentiometric sensor for heparin polyion: transient behavior and response mechanism. , 2007, Analytical chemistry.

[10]  Jidong Guo,et al.  Voltammetric heparin-selective electrode based on thin liquid membrane with conducting polymer-modified solid support. , 2006, Analytical chemistry.

[11]  W. Qin,et al.  Enhanced sensitivity electrochemical assay of low-molecular-weight heparins using rotating polyion-sensitive membrane electrodes , 2003, Analytical and bioanalytical chemistry.

[12]  Hsien-Chang Chang,et al.  Physical adsorption of protamine for heparin assay using a quartz crystal microbalance and electrochemical impedance spectroscopy , 2002 .

[13]  M. Meyerhoff,et al.  Rotating electrode potentiometry: lowering the detection limits of nonequilibrium polyion-sensitive membrane electrodes. , 2001, Analytical chemistry.

[14]  Ernö Pretsch,et al.  Lowering the detection limit of solvent polymeric ion-selective electrodes. 1. Modeling the influence of steady-state ion fluxes , 1999 .

[15]  E. Bakker,et al.  Influence of lipophilic inert electrolytes on the selectivity of polymer membrane electrodes. , 1998, Analytical chemistry.

[16]  M. Meyerhoff,et al.  Improved protamine-sensitive membrane electrode for monitoring heparin concentrations in whole blood via protamine titration. , 1998, Clinical chemistry.

[17]  H. Nam,et al.  One-component room temperature vulcanizing-type silicone rubber-based calcium-selective electrodes. , 1996, Analytical chemistry.

[18]  M. Meyerhoff,et al.  Extraction Thermodynamics of Polyanions into Plasticized Polymer Membranes Doped with Lipophilic Ion Exchangers: A Potentiometric Study , 1995 .

[19]  M. Meyerhoff,et al.  Response mechanism of polymer membrane-based potentiometric polyion sensors. , 1994, Analytical chemistry.

[20]  M. Meyerhoff,et al.  Electrochemical sensor for heparin: further characterization and bioanalytical applications. , 1993, Analytical chemistry.

[21]  S. Olson,et al.  Role of the antithrombin-binding pentasaccharide in heparin acceleration of antithrombin-proteinase reactions. Resolution of the antithrombin conformational change contribution to heparin rate enhancement. , 1992, The Journal of biological chemistry.

[22]  M. Meyerhoff,et al.  Heparin-responsive electrochemical sensor: a preliminary study. , 1992, Analytical chemistry.

[23]  M. Meyerhoff,et al.  Quantitative Determination of High Charge Density Polyanion Contaminants in Biomedical Heparin Preparations Using Potentiometric Polyanion Sensors. , 2010, Electroanalysis.

[24]  M. Meyerhoff,et al.  Protamine-sensitive polymer membrane electrode: characterization and bioanalytical applications. , 1995, Analytical biochemistry.