Bioplasmonic calligraphy for multiplexed label-free biodetection.

Printable multi-marker biochips that enable simultaneous quantitative detection of multiple target biomarkers in point-of-care and resource-limited settings are a holy grail in the field of biodiagnostics. However, preserving the functionality of biomolecules, which are routinely employed as recognition elements, during conventional printing approaches remains challenging. In this article, we introduce a simple yet powerful approach, namely plasmonic calligraphy, for realizing multiplexed label-free bioassays. Plasmonic calligraphy involves a regular ballpoint pen filled with biofunctionalized gold nanorods as plasmonic ink for creating isolated test domains on paper substrates. Biofriendly plasmonic calligraphy approach serves as a facile method to miniaturize the test domain size to few mm(2), which significantly improves the sensitivity of the plasmonic biosensor compared to bioplasmonic paper fabricated using immersion approach. Furthermore, plasmonic calligraphy also serves as a simple and efficient means to isolate multiple test domains on a single test strip, which facilitates multiplexed biodetection and multi-marker biochips. Plasmonic calligraphy, which can be potentially automated by implementing with a robotic arm, serves as an alternate path forward to overcome the limitations of conventional ink-jet printing.

[1]  G. Whitesides,et al.  Patterned paper as a platform for inexpensive, low-volume, portable bioassays. , 2007, Angewandte Chemie.

[2]  Limei Tian,et al.  Bioplasmonic paper as a platform for detection of kidney cancer biomarkers. , 2012, Analytical chemistry.

[3]  E. Kharasch,et al.  Urinary biomarkers for the early diagnosis of kidney cancer. , 2010, Mayo Clinic proceedings.

[4]  Limei Tian,et al.  Paper-based SERS swab for rapid trace detection on real-world surfaces. , 2010, ACS applied materials & interfaces.

[5]  R. V. Van Duyne,et al.  A nanoscale optical biosensor: sensitivity and selectivity of an approach based on the localized surface plasmon resonance spectroscopy of triangular silver nanoparticles. , 2002, Journal of the American Chemical Society.

[6]  C. Mirkin,et al.  Chemically isolating hot spots on concave nanocubes. , 2012, Nano letters.

[7]  Gregory G. Lewis,et al.  Quantifying analytes in paper-based microfluidic devices without using external electronic readers. , 2012, Angewandte Chemie.

[8]  Adam D. McFarland,et al.  A Nanoscale Optical Biosensor: Real-Time Immunoassay in Physiological Buffer Enabled by Improved Nanoparticle Adhesion , 2003 .

[9]  P Englebienne,et al.  Use of colloidal gold surface plasmon resonance peak shift to infer affinity constants from the interactions between protein antigens and antibodies specific for single or multiple epitopes. , 1998, The Analyst.

[10]  Claudio Parolo,et al.  Paper-based nanobiosensors for diagnostics. , 2013, Chemical Society reviews.

[11]  R. V. Van Duyne,et al.  A comparative analysis of localized and propagating surface plasmon resonance sensors: the binding of concanavalin a to a monosaccharide functionalized self-assembled monolayer. , 2004, Journal of the American Chemical Society.

[12]  S. Achilefu,et al.  Fluorescence Manipulation by Gold Nanoparticles: From Complete Quenching to Extensive Enhancement , 2011, Journal of nanobiotechnology.

[13]  Xu Li,et al.  A perspective on paper-based microfluidics: Current status and future trends. , 2012, Biomicrofluidics.

[14]  Hongli Zhu,et al.  Highly transparent and flexible nanopaper transistors. , 2013, ACS nano.

[15]  Jianfang Wang,et al.  Shape- and size-dependent refractive index sensitivity of gold nanoparticles. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[16]  Lu-Lu Qu,et al.  Batch fabrication of disposable screen printed SERS arrays. , 2012, Lab on a chip.

[17]  J. Hafner,et al.  Localized surface plasmon resonance sensors. , 2011, Chemical reviews.

[18]  G. Whitesides,et al.  Understanding wax printing: a simple micropatterning process for paper-based microfluidics. , 2009, Analytical chemistry.

[19]  L. Lechuga,et al.  LSPR-based nanobiosensors , 2009 .

[20]  Chad A Mirkin,et al.  Nanostructures in biodiagnostics. , 2005, Chemical reviews.

[21]  C. Murphy,et al.  Quantitation of metal content in the silver-assisted growth of gold nanorods. , 2006, The journal of physical chemistry. B.

[22]  G. Whitesides,et al.  Low-cost printing of poly(dimethylsiloxane) barriers to define microchannels in paper. , 2008, Analytical chemistry.

[23]  S. Maier,et al.  Plasmonics: Localization and guiding of electromagnetic energy in metal/dielectric structures , 2005 .

[24]  Xiaohua Huang,et al.  Gold Nanorods: From Synthesis and Properties to Biological and Biomedical Applications , 2009, Advanced materials.

[25]  Wei Shen,et al.  Progress in patterned paper sizing for fabrication of paper-based microfluidic sensors , 2010 .

[26]  G. Whitesides,et al.  Diagnostics for the developing world: microfluidic paper-based analytical devices. , 2010, Analytical chemistry.

[27]  Peter Kauffman,et al.  Microfluidics without pumps: reinventing the T-sensor and H-filter in paper networks. , 2010, Lab on a chip.

[28]  Limei Tian,et al.  Gold nanorods as plasmonic nanotransducers: distance-dependent refractive index sensitivity. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[29]  Jeffrey N. Anker,et al.  Biosensing with plasmonic nanosensors. , 2008, Nature materials.

[30]  S. T. Phillips,et al.  Metering the capillary-driven flow of fluids in paper-based microfluidic devices. , 2010, Analytical chemistry.

[31]  Emanuel Carrilho,et al.  Paper-based ELISA. , 2010, Angewandte Chemie.

[32]  D. Citterio,et al.  Inkjet-printed microfluidic multianalyte chemical sensing paper. , 2008, Analytical chemistry.

[33]  S. Singamaneni,et al.  Gold nanorods as nanotransducers to monitor the growth and swelling of ultrathin polymer films , 2012, Nanotechnology.

[34]  J. Olkkonen,et al.  Flexographically printed fluidic structures in paper. , 2010, Analytical chemistry.

[35]  Joseph M Slocik,et al.  Multifunctional analytical platform on a paper strip: separation, preconcentration, and subattomolar detection. , 2013, Analytical chemistry.

[36]  Adam Wax,et al.  Rational Selection of Gold Nanorod Geometry for Label-Free Plasmonic Biosensors , 2009, ACS nano.

[37]  Limei Tian,et al.  Hot Spot‐Localized Artificial Antibodies for Label‐Free Plasmonic Biosensing , 2013, Advanced functional materials.

[38]  P. Pellegrino,et al.  Highly sensitive surface enhanced Raman scattering substrates based on filter paper loaded with plasmonic nanostructures. , 2011, Analytical chemistry.

[39]  Wei W. Yu,et al.  Inkjet-printed paper-based SERS dipsticks and swabs for trace chemical detection. , 2013, The Analyst.

[40]  Luis M. Liz-Marzán,et al.  Silica-Coating and Hydrophobation of CTAB-Stabilized Gold Nanorods , 2006 .

[41]  Mikael Käll,et al.  Refractometric sensing using propagating versus localized surface plasmons: a direct comparison. , 2009, Nano letters.

[42]  Paul M. Pellegrino,et al.  Biomimetic SERS substrate: peptide recognition elements for highly selective chemical detection in chemically complex media , 2013 .

[43]  J. Lewis,et al.  Pen‐on‐Paper Flexible Electronics , 2011, Advanced materials.

[44]  D. Reinhoudt,et al.  Fluorescence quenching of dye molecules near gold nanoparticles: radiative and nonradiative effects. , 2002, Physical review letters.

[45]  R. V. Van Duyne,et al.  Detection of a biomarker for Alzheimer's disease from synthetic and clinical samples using a nanoscale optical biosensor. , 2005, Journal of the American Chemical Society.

[46]  M. McConney,et al.  Nanorod decorated nanowires as highly efficient SERS-active hybrids , 2011 .