Molecularly imprinted electrochemical sensing of urinary melatonin in a microfluidic system.

Melatonin levels may be related to the risks of breast cancer and prostate cancer. The measurement of urinary melatonin is also useful in monitoring serum melatonin levels following oral administration. In this work, melatonin is the target molecule, which is imprinted onto poly(ethylene-co-vinyl alcohol) by evaporation of the solvent on the working electrode of an electrochemical sensing chip. This sensing chip is used directly as a tool for optimizing the imprinting polymer composition, flow rate, and injection volume of the samples. Microfluidic sensing of the target and interference molecules revealed that the lowest detection limit is as low as ∼pM, and the electrochemical response is weak even at high interference concentrations. Poly(ethylene-co-vinyl alcohol), containing 44 mol. % ethylene, had an imprinting effectiveness of more than six-fold. In random urine analysis, the microfluidic amperometric measurements of melatonin levels with an additional and recovery of melatonin, the melatonin recovery achieved 94.78 ± 1.9% for melatonin at a concentration of 1.75-2.11 pg/mL.

[1]  Andreas Manz,et al.  Chip-based microsystems for genomic and proteomic analysis , 2000 .

[2]  M. Bowyer,et al.  Molecularly imprinted polymers (MIPs): sensing, an explosive new opportunity? , 2007, Organic & biomolecular chemistry.

[3]  Susan E Hankinson,et al.  Urinary melatonin levels and breast cancer risk. , 2005, Journal of the National Cancer Institute.

[4]  Chun-Yueh Huang,et al.  Integrated potentiostat for electrochemical sensing of urinary 3-hydroxyanthranilic acid with molecularly imprinted poly(ethylene-co-vinyl alcohol). , 2015, Biosensors & bioelectronics.

[5]  C. Alonso-González,et al.  Melatonin–estrogen interactions in breast cancer , 2005, Journal of pineal research.

[6]  Alexander Revzin,et al.  Electrochemical biosensors for on-chip detection of oxidative stress from immune cells. , 2011, Biomicrofluidics.

[7]  T. Prasada Rao,et al.  Potentiometric transducer based biomimetic sensors for priority envirotoxic markers--an overview. , 2008, Talanta.

[8]  Ronen Polsky,et al.  Integrated carbon fiber electrodes within hollow polymer microneedles for transdermal electrochemical sensing. , 2011, Biomicrofluidics.

[9]  F. Waldhauser,et al.  Measurement of urinary melatonin: a useful tool for monitoring serum melatonin after its oral administration. , 2000, The Journal of clinical endocrinology and metabolism.

[10]  Andrew J deMello,et al.  Micro- and nanofluidic systems for high-throughput biological screening. , 2009, Drug discovery today.

[11]  Tse-Chuan Chou,et al.  A portable potentiostat for the bilirubin-specific sensor prepared from molecular imprinting. , 2007, Biosensors & bioelectronics.

[12]  James L. Thomas,et al.  Sensing of digestive proteins in saliva with a molecularly imprinted poly(ethylene-co-vinyl alcohol) thin film coated quartz crystal microbalance sensor. , 2011, ACS applied materials & interfaces.

[13]  A. Revzin,et al.  Biosensors for immune cell analysis-A perspective. , 2012, Biomicrofluidics.

[14]  Sergey A. Piletsky,et al.  Electrochemical Sensors Based on Molecularly Imprinted Polymers , 2002 .

[15]  C. Ayela,et al.  Micro and nanofabrication of molecularly imprinted polymers. , 2012, Topics in current chemistry.

[16]  Nicola Elvassore,et al.  Flow biosensing and sampling in indirect electrochemical detection. , 2012, Biomicrofluidics.

[17]  Frank B. Hu,et al.  Melatonin secretion and the incidence of type 2 diabetes. , 2013, JAMA.

[18]  A. Scates,et al.  Melatonin Treatment for Insomnia in Pediatric Patients with Attention-Deficit/Hyperactivity Disorder , 2010, The Annals of pharmacotherapy.

[19]  G. Bellipanni,et al.  Effects of Melatonin in Perimenopausal and Menopausal Women: Our Personal Experience , 2005, Annals of the New York Academy of Sciences.

[20]  Wei-Ming Yeh,et al.  A microfluidic system utilizing molecularly imprinted polymer films for amperometric detection of morphine , 2007 .

[21]  S. Shiu,et al.  Melatonin and prostate cancer cell proliferation: Interplay with castration, epidermal growth factor, and androgen sensitivity , 2002, The Prostate.

[22]  Ying-Zong Juang,et al.  Optical sensing of urinary melatonin with molecularly imprinted poly(ethylene-co-vinyl alcohol) coated zinc oxide nanorod arrays. , 2013, Biosensors & bioelectronics.

[23]  R. Zare,et al.  Surface-imprinted polymers in microfluidic devices , 2012, Science China Chemistry.

[24]  Arturo J. Miranda-Ordieres,et al.  Electrochemical sensors based on molecularly imprinted polymers , 2004 .

[25]  K. Ho,et al.  Molecularly Imprinted Electrochemical Sensors , 2010 .

[26]  D. Cliffel,et al.  Electrochemical sensors and biosensors. , 2012, Analytical chemistry.

[27]  Hung-Yin Lin,et al.  Urinalysis with molecularly imprinted poly(ethylene-co-vinyl alcohol) potentiostat sensors. , 2009, Biosensors & bioelectronics.