High-frequency phase shift measurement greatly enhances the sensitivity of QCM immunosensors.

In spite of being widely used for in liquid biosensing applications, sensitivity improvement of conventional (5-20MHz) quartz crystal microbalance (QCM) sensors remains an unsolved challenging task. With the help of a new electronic characterization approach based on phase change measurements at a constant fixed frequency, a highly sensitive and versatile high fundamental frequency (HFF) QCM immunosensor has successfully been developed and tested for its use in pesticide (carbaryl and thiabendazole) analysis. The analytical performance of several immunosensors was compared in competitive immunoassays taking carbaryl insecticide as the model analyte. The highest sensitivity was exhibited by the 100MHz HFF-QCM carbaryl immunosensor. When results were compared with those reported for 9MHz QCM, analytical parameters clearly showed an improvement of one order of magnitude for sensitivity (estimated as the I50 value) and two orders of magnitude for the limit of detection (LOD): 30μgl(-1) vs 0.66μgL(-1)I50 value and 11μgL(-1) vs 0.14μgL(-1) LOD, for 9 and 100MHz, respectively. For the fungicide thiabendazole, I50 value was roughly the same as that previously reported for SPR under the same biochemical conditions, whereas LOD improved by a factor of 2. The analytical performance achieved by high frequency QCM immunosensors surpassed those of conventional QCM and SPR, closely approaching the most sensitive ELISAs. The developed 100MHz QCM immunosensor strongly improves sensitivity in biosensing, and therefore can be considered as a very promising new analytical tool for in liquid applications where highly sensitive detection is required.

[1]  Y. Okahata,et al.  A versatile planar QCM-based sensor design for nonlabeling biomolecule detection. , 2002, Analytical chemistry.

[2]  Reinhard Schwödiauer,et al.  High frequency QCM based sensor system for sensitive detection of dissolved analytes , 2010 .

[3]  Abiche H. Dewilde,et al.  Quartz crystal microbalance measurements of mitochondrial depolarization predicting chemically induced toxicity of vascular cells and macrophages. , 2013, Analytical biochemistry.

[4]  Christopher M. Yip,et al.  Operation of an ultrasensitive 30-MHz quartz crystal microbalance in liquids , 1993 .

[5]  George Papadakis,et al.  Quantitative determination of size and shape of surface-bound DNA using an acoustic wave sensor. , 2008, Biophysical journal.

[6]  Yolanda Jiménez,et al.  A piezoelectric immunosensor for the determination of pesticide residues and metabolites in fruit juices. , 2009, Talanta.

[7]  K. Marx The Quartz Crystal Microbalance and the Electrochemical QCM: Applications to Studies of Thin Polymer Films, Electron Transfer Systems, Biological Macromolecules, Biosensors, and Cells , 2006 .

[8]  Angel Montoya,et al.  Development of an enzyme-linked immunosorbent assay to carbaryl. 1. Antibody production from several haptens and characterization in different immunoassay formats , 1997 .

[9]  W. H. King Piezoelectric Sorption Detector. , 1964 .

[10]  Reinhard Schwödiauer,et al.  User-friendly, miniature biosensor flow cell for fragile high fundamental frequency quartz crystal resonators. , 2009, Biosensors & bioelectronics.

[11]  G. Sauerbrey Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung , 1959 .

[12]  Konstantinos Mitsakakis,et al.  Detection of multiple cardiac markers with an integrated acoustic platform for cardiovascular risk assessment. , 2011, Analytica chimica acta.

[13]  J. Mandel,et al.  Ultrasensitive quartz crystal microbalance sensors for detection of M13-Phages in liquids. , 2001, Biosensors & bioelectronics.

[14]  A. Abad,et al.  Development of an Enzyme-Linked Immunosorbent Assay to Carbaryl. 2. Assay Optimization and Application to the Analysis of Water Samples , 1997 .

[15]  Y. Okahata,et al.  Small mass-change detectable quartz crystal microbalance and its application to enzymatic one-base elongation on DNA. , 2011, Analytical chemistry.

[16]  Stephanus Büttgenbach,et al.  Development and application of a miniaturised quartz crystal microbalance (QCM) as immunosensor for bone morphogenetic protein-2 , 2005 .

[17]  A. M. Escuela,et al.  Indirect competitive immunoassay for the detection of fungicide Thiabendazole in whole orange samples by Surface Plasmon Resonance. , 2012, The Analyst.

[18]  J. Gordon,et al.  The oscillation frequency of a quartz resonator in contact with liquid , 1985 .

[19]  N. K. Chaki,et al.  Self-assembled monolayers as a tunable platform for biosensor applications. , 2002, Biosensors & bioelectronics.

[20]  Srinivas Tadigadapa,et al.  Human serum albumin adsorption study on 62-MHz miniaturized quartz gravimetric sensors. , 2008, Analytical chemistry.

[21]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[22]  K. Marx,et al.  Quartz crystal microbalance: a useful tool for studying thin polymer films and complex biomolecular systems at the solution-surface interface. , 2003, Biomacromolecules.

[23]  M. Moreno,et al.  Determination of thiabendazole in fruit juices by a new monoclonal enzyme immunoassay. , 2001, Journal of AOAC International.

[24]  Matthew A Cooper,et al.  A Survey of the 2010 Quartz Crystal Microbalance Literature , 2012, Journal of molecular recognition : JMR.

[25]  Jing Zhang,et al.  An Experimental Study on Fabricating an Inverted Mesa-Type Quartz Crystal Resonator Using a Cheap Wet Etching Process , 2013, Sensors.

[26]  G. Sauerbrey,et al.  Use of quartz vibration for weighing thin films on a microbalance , 1959 .

[27]  Yolanda Jiménez,et al.  Validation of a Phase-Mass Characterization Concept and Interface for Acoustic Biosensors , 2011, Sensors.

[28]  L M Lechuga,et al.  Determination of carbaryl in natural water samples by a surface plasmon resonance flow-through immunosensor. , 2006, Biosensors & bioelectronics.