Selective electrochemical sensing of glycated hemoglobin (HbA1c) on thiophene-3-boronic acid self-assembled monolayer covered gold electrodes.

We report a novel concept of sensing glycated hemoglobin, HbA 1c, which is now the most important index for a long-term average blood glucose level, by first selectively immobilizing it on the thiophene-3-boronic acid (T3BA) self-assembled monolayer (SAM)-covered gold electrode by a selective chemical reaction with boronic acid. HbA 1c thus immobilized is then detected by the label-free electrochemical impedance spectroscopic (EIS) measurements with a redox probe, an equimolar mixture of K 3Fe(CN) 6 and K 4Fe(CN) 6, present. The rate of charge transfer between the electrode and the redox probe is shown to be modulated by the amount of HbA 1c in the matrix hemoglobin solution due to the blocking effect caused by the binding of HbA 1c with boronic acid. Both the formation of a well-defined T3BA-SAM on the gold surface and the chemical binding of its boronic acid with HbA 1c in solution were confirmed by quartz crystal microbalance, atomic force microscopy, and EIS experiments.

[1]  M. Landt,et al.  HPLC detection of fetal blood in meconium: improved sensitivity compared with qualitative methods. , 1998, Clinical chemistry.

[2]  Su-Moon Park,et al.  Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy. , 2006, The journal of physical chemistry. B.

[3]  K. Ikeda,et al.  Determination of glycated albumin by enzyme-linked boronate immunoassay (ELBIA). , 1998, Clinical chemistry.

[4]  Jan Halámek,et al.  Development of a biosensor for glycated hemoglobin , 2007 .

[5]  R. Schmid,et al.  Quantitative measurement of HbA1c by an immunoturbidimetric assay compared to a standard HPLC method. , 1995, American journal of clinical pathology.

[6]  Byeang Hyean Kim,et al.  Label-free detection of antibody-antigen interactions on (R)-lipo-diaza-18-crown-6 self-assembled monolayer modified gold electrodes. , 2008, Analytical chemistry.

[7]  D. Katritsis,et al.  Measurement of glycated hemoglobin (HbA1c) with an automated POCT instrument in comparison with HPLC and automated immunochemistry method: evaluation of the influence of hemoglobin variants , 2006, Clinical chemistry and laboratory medicine.

[8]  F. Frantzen,et al.  Soluble highly coloured phenylboronic acids and their use in glycohemoglobin quantification. , 1997, Clinica chimica acta; international journal of clinical chemistry.

[9]  Su-Moon Park,et al.  Label-free detection of DNA molecules on the dendron based self-assembled monolayer by electrochemical impedance spectroscopy. , 2008, Analytica chimica acta.

[10]  W. G. John,et al.  A reliable non-separation fluorescence quenching assay for total glycated serum protein: a simple alternative to nitroblue tetrazolium reduction , 2000, Annals of clinical biochemistry.

[11]  Su-Moon Park,et al.  Electrochemistry of Guest Molecules in Thiolated Cyclodextrin Self-Assembled Monolayers: An Implication for Size-Selective Sensors , 1998 .

[12]  J. Hemminger,et al.  Formation of a Self-Assembled Monolayer by Adsorption of Thiophene on Au(111) and Its Photooxidation , 1996 .

[13]  T Tanaka,et al.  Detection of HbA(1c) by boronate affinity immunoassay using bacterial magnetic particles. , 2001, Biosensors & bioelectronics.

[14]  Su-Moon Park,et al.  Electrochemical sensor for electrochemically inactive β-D(+)-glucose using α-cyclodextrin template molecules , 2002 .

[15]  Yoo,et al.  An electrochemical impedance measurement technique employing Fourier transform , 2000, Analytical chemistry.

[16]  E. Sacher,et al.  A theoretical investigation of the interactions between thiophene and vanadium, chromium, copper, and gold , 1995 .

[17]  Su-Moon Park,et al.  Determination of electron transfer kinetic parameters by fourier transform electrochemical impedance spectroscopic analysis. , 2006, The journal of physical chemistry. B.

[18]  Byung-Cheol Kim,et al.  Molecular recognition of protonated polyamines at calix[4]crown-5 self-assembled monolayer modified electrodes by impedance measurements. , 2007, Analytical chemistry.

[19]  Byoung-Yong Chang,et al.  Fourier transform analysis of chronoamperometric currents obtained during staircase voltammetric experiments. , 2007, Analytical chemistry.

[20]  S. Blincko,et al.  Measurement of Glycated Haemoglobin in whole Blood by a Novel Fluorescence Quenching Assay , 2000, Annals of clinical biochemistry.

[21]  Donald D. Johnson,et al.  An efficient preparation of polyanionic affinity agent and its evaluation for the measurement of glycated hemoglobin. , 2005, Bioorganic & medicinal chemistry.

[22]  D. Nathan,et al.  Relationship between glycated haemoglobin levels and mean glucose levels over time , 2007, Diabetologia.

[23]  M G Scott,et al.  Hemoglobin Raleigh as the cause of a falsely increased hemoglobin A1C in an automated ion-exchange HPLC method. , 1998, Clinical chemistry.

[24]  J. Jeppsson,et al.  Improved Method for Analysis of Glycated Haemoglobin by Ion Exchange Chromatography , 1994, Annals of clinical biochemistry.

[25]  Su-Moon Park,et al.  Novel instrumentation in electrochemical impedance spectroscopy and a full description of an electrochemical system , 2006 .

[26]  Immunoturbidimetric assay of glycated hemoglobin , 1999, Journal of clinical laboratory analysis.

[27]  L. Wan,et al.  Phase transition of thiophene molecules on Au(111) in solution , 2003 .

[28]  Mina Okochi,et al.  Electrochemical detection of HbA1c, a maker for diabetes, using a flow immunoassay system , 2007 .

[29]  F Frantzen,et al.  Glycohemoglobin filter assay for doctors' offices based on boronic acid affinity principle. , 1997, Clinical chemistry.

[30]  Y. Ohta,et al.  Atomic force microscopic observation of mechanically traumatized erythrocytes. , 2002, Artificial organs.

[31]  S. Blincko,et al.  Non-separation assay for glycohemoglobin. , 1998, Clinical chemistry.

[32]  M. Jenkins,et al.  Capillary Electrophoresis of Hemoglobin , 2003, Clinical chemistry and laboratory medicine.

[33]  Petr Skládal,et al.  Development of a combined setup for simultaneous detection of total and glycated haemoglobin content in blood samples. , 2006, Biosensors & bioelectronics.

[34]  Byoung-Yong Chang,et al.  Integrated description of electrode/electrolyte interfaces based on equivalent circuits and its verification using impedance measurements. , 2006, Analytical chemistry.