Superwettable Electrochemical Biosensor toward Detection of Cancer Biomarkers.

Bioinspired superwettable micropatterns that combine two extreme states of superhydrophobicity and superhydrophilicity with the ability to enrich and absorb microdroplets are suitable for versatile and robust sensing applications. Here we introduce a superwettable microchip that integrates superhydrophobic-superhydrophilic micropatterns and a nanodendritic electrochemical biosensor toward the detection of prostate cancer biomarkers. On the superwettable microchip, the superhydrophobic area could confine the microdroplets in superhydrophilic microwells; such behavior is extremely helpful for reducing the amount of analytical solution. In contrast, superhydrophilic microwells exhibit a high adhesive force toward microdroplets, and the nanodendritic structures can improve probe-binding capacity and response signals, thus greatly enhancing the sensitivity. Sensitive and selective detection of prostate cancer biomarkers including miRNA-375, miRNA-141, and prostate-specific antigen on a single microchip is also achieved. Such a superwettable microchip with high sensitivity, low sample volume, and upside-down detection capability in a single microdroplet shows great potential to fabricate portable devices toward complex biosensing applications.

[1]  Yuanjin Zhao,et al.  Emerging Droplet Microfluidics. , 2017, Chemical reviews.

[2]  Wanxin Shi,et al.  Superhydrophilic cotton thread with temperature-dependent pattern for sensitive nucleic acid detection. , 2016, Biosensors & bioelectronics.

[3]  Hyunchul Kim,et al.  Bio-Inspired Extreme Wetting Surfaces for Biomedical Applications , 2016, Materials.

[4]  Aicheng Chen,et al.  Nanomaterials Based Electrochemical Sensors for Biomedical Applications , 2013 .

[5]  Carmen Alvarez-Lorenzo,et al.  Superhydrophobic chips for cell spheroids high-throughput generation and drug screening. , 2014, ACS applied materials & interfaces.

[6]  Chunhai Fan,et al.  Electrochemical interrogation of conformational changes as a reagentless method for the sequence-specific detection of DNA , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[7]  Shana O Kelley,et al.  Programming the detection limits of biosensors through controlled nanostructuring. , 2009, Nature nanotechnology.

[8]  Erkang Wang,et al.  Functionalization of monolithic and porous three-dimensional graphene by one-step chitosan electrodeposition for enzymatic biosensor. , 2014, ACS applied materials & interfaces.

[9]  Gao Yang,et al.  Ultratrace DNA Detection Based on the Condensing‐Enrichment Effect of Superwettable Microchips , 2015, Advanced materials.

[10]  J. Garcia-Cordero,et al.  Evaporation-Driven Bioassays in Suspended Droplets. , 2016, Analytical chemistry.

[11]  Doris Vollmer,et al.  Candle Soot as a Template for a Transparent Robust Superamphiphobic Coating , 2012, Science.

[12]  Shufeng Zhou,et al.  Electrochemical hydrogen sulfide biosensors. , 2016, The Analyst.

[13]  Zhifang Fan,et al.  Sessile droplets for chemical and biological assays. , 2017, Lab on a chip.

[14]  David Reinhoudt,et al.  What do we need for a superhydrophobic surface? A review on the recent progress in the preparation of superhydrophobic surfaces. , 2007, Chemical Society reviews.

[15]  Yanlei Yu,et al.  Photocontrol of fluid slugs in liquid crystal polymer microactuators , 2016, Nature.

[16]  Xiangheng Niu,et al.  Novel snowflake-like Pt-Pd bimetallic clusters on screen-printed gold nanofilm electrode for H2O2 and glucose sensing. , 2012, Biosensors & bioelectronics.

[17]  J. Mano,et al.  Screening of Nanocomposite Scaffolds Arrays Using Superhydrophobic‐Wettable Micropatterns , 2017 .

[18]  Tingting Ren,et al.  Paper‐Based Hydrophobic/Lipophobic Surface for Sensing Applications Involving Aggressive Liquids , 2016 .

[19]  Y. Ito,et al.  Surface micropatterning to regulate cell functions. , 1999, Biomaterials.

[20]  Benoît Piro,et al.  Recent Advances in Electrochemical Immunosensors , 2017, Sensors.

[21]  Joseph Wang Electrochemical glucose biosensors. , 2008, Chemical reviews.

[22]  Y. Wen,et al.  Cell micropatterns based on silicone-oil-modified slippery surfaces. , 2016, Nanoscale.

[23]  Tony M. Yen,et al.  Self-Assembled Pico-Liter Droplet Microarray for Ultrasensitive Nucleic Acid Quantification. , 2015, ACS nano.

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

[25]  Yuandong Zhao,et al.  Recent advances in electrochemical sensing for hydrogen peroxide: a review. , 2012, The Analyst.

[26]  Robin H. A. Ras,et al.  Moving superhydrophobic surfaces toward real-world applications , 2016, Science.

[27]  Jin Zhai,et al.  Directional water collection on wetted spider silk , 2010, Nature.

[28]  Dayeong Kim,et al.  A Droplet-Based High-Throughput SERS Platform on a Droplet-Guiding-Track-Engraved Superhydrophobic Substrate. , 2017, Small.

[29]  Shana O Kelley,et al.  An electrochemical clamp assay for direct, rapid analysis of circulating nucleic acids in serum. , 2015, Nature chemistry.

[30]  Gengfeng Zheng,et al.  Multiplexed electrical detection of cancer markers with nanowire sensor arrays , 2005, Nature Biotechnology.

[31]  Sam Emaminejad,et al.  Fully integrated wearable sensor arrays for multiplexed in situ perspiration analysis , 2016, Nature.

[32]  Lei Jiang,et al.  Bioinspired Surfaces with Superwettability: New Insight on Theory, Design, and Applications. , 2015, Chemical reviews.

[33]  Yu Qin,et al.  Functional nanoprobes for ultrasensitive detection of biomolecules. , 2010, Chemical Society reviews.

[34]  Zhiyong Tang,et al.  Application of Au based nanomaterials in analytical science , 2017 .

[35]  F. Hamdy,et al.  Changes in circulating microRNA levels associated with prostate cancer , 2012, British Journal of Cancer.

[36]  Joanna Aizenberg,et al.  Design of anti-icing surfaces: smooth, textured or slippery? , 2016 .

[37]  Shutao Wang,et al.  Superwettable Microchips as a Platform toward Microgravity Biosensing. , 2017, ACS nano.

[38]  Xiaoyuan Li,et al.  Polyelectrolyte multilayer as matrix for electrochemical deposition of gold clusters: toward super-hydrophobic surface. , 2004, Journal of the American Chemical Society.

[39]  A. Efremov,et al.  Micropatterned superhydrophobic structures for the simultaneous culture of multiple cell types and the study of cell-cell communication. , 2013, Biomaterials.

[40]  P. Levkin,et al.  A Facile Approach to Superhydrophilic–Superhydrophobic Patterns in Porous Polymer Films , 2011, Advanced materials.

[41]  João F. Mano,et al.  Fabrication of Hydrogel Particles of Defined Shapes Using Superhydrophobic‐Hydrophilic Micropatterns , 2016, Advanced materials.

[42]  Yanlin Song,et al.  Bio-inspired photonic-crystal microchip for fluorescent ultratrace detection. , 2014, Angewandte Chemie.

[43]  P. Levkin,et al.  Droplet‐Array (DA) Sandwich Chip: A Versatile Platform for High‐Throughput Cell Screening Based on Superhydrophobic–Superhydrophilic Micropatterning , 2015, Advanced materials.

[44]  Yanlin Song,et al.  Hydrophilic-Hydrophobic Patterned Molecularly Imprinted Photonic Crystal Sensors for High-Sensitive Colorimetric Detection of Tetracycline. , 2015, Small.

[45]  Andrea Toma,et al.  Breaking the diffusion limit with super-hydrophobic delivery of molecules to plasmonic nanofocusing SERS structures , 2011 .

[46]  Shufeng Zhou,et al.  Electrochemical Sensors for Nitric Oxide Detection in Biological Applications , 2014 .

[47]  T. G. Drummond,et al.  Electrochemical DNA sensors , 2003, Nature Biotechnology.

[48]  Christophe Clanet,et al.  Water impacting on superhydrophobic macrotextures , 2015, Nature Communications.

[49]  Yanlin Song,et al.  Patterning of controllable surface wettability for printing techniques. , 2013, Chemical Society reviews.

[50]  T. Darmanin,et al.  Recent advances in designing superhydrophobic surfaces. , 2013, Journal of colloid and interface science.

[51]  J Waxman,et al.  Circulating microRNAs as potential new biomarkers for prostate cancer , 2013, British Journal of Cancer.

[52]  Hanqing Yu,et al.  Hydrophobic Teflon films as concentrators for single-molecule SERS detection , 2012 .

[53]  Akira Fujishima,et al.  Patterning of a colloidal crystal film on a modified hydrophilic and hydrophobic surface. , 2002, Angewandte Chemie.

[54]  P. Levkin,et al.  Emerging Applications of Superhydrophilic‐Superhydrophobic Micropatterns , 2013, Advanced materials.

[55]  Mingjie Liu,et al.  Nature-inspired superwettability systems , 2017 .

[56]  Anthony Turner,et al.  Cancer Detection Using Nanoparticle-Based Sensors , 2012 .

[57]  U. Liebel,et al.  Superhydrophobic-superhydrophilic micropatterning: towards genome-on-a-chip cell microarrays. , 2011, Angewandte Chemie.

[58]  A. Fujishima,et al.  Superhydrophobic TiO2 Surfaces: Preparation, Photocatalytic Wettability Conversion, and Superhydrophobic-Superhydrophilic Patterning , 2007 .

[59]  Yolonda L Colson,et al.  Superhydrophobic materials for biomedical applications. , 2016, Biomaterials.