Silicon Microcantilever Sensors to Detect the Reversible Conformational Change of a Molecular Switch, Spiropyan

The high sensitivity of silicon microcantilever sensors has expanded their use in areas ranging from gas sensing to bio-medical applications. Photochromic molecules also represent promising candidates for a large variety of sensing applications. In this work, the operating principles of these two sensing methods are combined in order to detect the reversible conformational change of a molecular switch, spiropyran. Thus, arrays of silicon microcantilever sensors were functionalized with spiropyran on the gold covered side and used as test microcantilevers. The microcantilever deflection response was observed, in five sequential cycles, as the transition from the spiropyran (SP) (CLOSED) to the merocyanine (MC) (OPEN) state and vice-versa when induced by UV and white light LED sources, respectively, proving the reversibility capabilities of this type of sensor. The microcantilever deflection direction was observed to be in one direction when changing to the MC state and in the opposite direction when changing back to the SP state. A tensile stress was induced in the microcantilever when the SP to MC transition took place, while a compressive stress was observed for the reverse transition. These different type of stresses are believed to be related to the spatial conformational changes induced in the photochromic molecule upon photo-isomerisation.

[1]  D. Chung,et al.  Preparation of porous membranes grafted with poly(spiropyran‐containing methacrylate) and photocontrol of permeability , 1994 .

[2]  Rafal Klajn,et al.  Spiropyran-based dynamic materials. , 2014, Chemical Society reviews.

[3]  Philip Kim,et al.  Directing and sensing changes in molecular conformation on individual carbon nanotube field effect transistors. , 2005, Journal of the American Chemical Society.

[4]  Tao Chen,et al.  Glucose-responsive polymer brushes for microcantilever sensing , 2010 .

[5]  M. Hegner,et al.  Specific antigen/antibody interactions measured by force microscopy. , 1996, Biophysical journal.

[6]  Laura M. Lechuga,et al.  Nanomechanical biosensors: a new sensing tool , 2006 .

[7]  S. Giordani,et al.  Interaction studies between photochromic spiropyrans and transition metal cations: the curious case of copper. , 2012, Organic & biomolecular chemistry.

[8]  Frank Jahnke,et al.  Photon-Modulated Wettability Changes on Spiropyran-Coated Surfaces , 2002 .

[9]  Dermot Diamond,et al.  Spiropyran modified micro-fluidic chip channels as photonically controlled self-indicating system for metal ion accumulation and release , 2009 .

[10]  An optimized measurement chamber for cantilever array measurements in liquid incorporating an automated sample handling system , 2015 .

[11]  P. De Los Rios,et al.  Real-Time Monitoring of Protein Conformational Changes Using a Nano-Mechanical Sensor , 2014, PloS one.

[12]  A. Keating,et al.  MEMS based hydrogen sensing with parts-per-billion resolution , 2019, Sensors and Actuators B: Chemical.

[13]  Dermot Diamond,et al.  Micro-Capillary Coatings Based on Spiropyran Polymeric Brushes for Metal Ion Binding, Detection, and Release in Continuous Flow , 2018, Sensors.

[14]  Sandeep Kumar Vashist,et al.  Microcantilevers for Sensing Applications , 2010 .

[15]  G. Wallace,et al.  Optical switching of protein interactions on photosensitive-electroactive polymers measured by atomic force microscopy. , 2013, Journal of materials chemistry. B.

[16]  Chao Gao,et al.  Humidity sensors based on AlN microcantilevers excited at high-order resonant modes and sensing layers of uniform graphene oxide , 2019, Sensors and Actuators B: Chemical.

[17]  Z. C. Alex,et al.  A study and analysis of Microcantilever materials for disease detection , 2018 .

[18]  J. Pascual,et al.  Induction of a photostationary ring-opening-ring-closing state of spiropyran monolayers on the semimetallic Bi(110) surface. , 2012, Physical review letters.

[19]  Dong-weon Lee,et al.  Fully automated high-throughput cardiac toxicity screening platform using interlocking-structured 192 SU-8 cantilever arrays , 2019, Sensors and Actuators B: Chemical.

[20]  Martin Hegner,et al.  Label free analysis of transcription factors using microcantilever arrays. , 2006, Biosensors & bioelectronics.

[21]  D. Diamond,et al.  Self-protonating spiropyran-co-NIPAM-co-acrylic acid hydrogel photoactuators , 2013 .

[22]  R. Haag,et al.  Reversible electron-induced cis–trans isomerization mediated by intermolecular interactions , 2012, Journal of physics. Condensed matter : an Institute of Physics journal.

[23]  G. Glasser,et al.  Direct measurement of the dipole moment of a metastable merocyanine by electromechanical interferometry , 1997 .

[24]  Z. Tan,et al.  Interactions of single-stranded DNA on microcantilevers , 2011 .

[25]  H. Lang,et al.  Chapter 11 - Biological Single Molecule Applications and Advanced Biosensing , 2003 .

[26]  D. Diamond,et al.  Spiropyran polymeric microcapillary coatings for photodetection of solvent polarity. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[27]  A. Boisen,et al.  Cantilever-like micromechanical sensors , 2011 .

[28]  Martin Hegner,et al.  Conformational change of bacteriorhodopsin quantitatively monitored by microcantilever sensors. , 2006, Biophysical journal.

[29]  Nai-Kuan Chou,et al.  A Wireless Bio-MEMS Sensor for C-Reactive Protein Detection Based on Nanomechanics , 2006, IEEE Transactions on Biomedical Engineering.

[30]  Martin Hegner,et al.  Nanomechanical Cantilever Array Sensors , 2017, Springer Handbook of Nanotechnology.

[31]  F. Lyng,et al.  Microcantilever arrays functionalised with spiropyran photoactive moieties as systems to measure photo-induced surface stress changes , 2016 .

[32]  Scott R White,et al.  Mechanophore-linked addition polymers. , 2007, Journal of the American Chemical Society.

[33]  M. Jakobsen,et al.  Investigations on antibody binding to a micro-cantilever coated with a BAM pesticide residue , 2011, Nanoscale research letters.

[34]  D. Diamond,et al.  Photo-Responsive Polymeric Structures Based on Spiropyran , 2012 .

[35]  P. Xu,et al.  Detection of volatile-organic-compounds (VOCs) in solution using cantilever-based gas sensors. , 2018, Talanta.

[36]  Jilin Tang,et al.  Label-free detection of kanamycin using aptamer-based cantilever array sensor. , 2014, Biosensors & bioelectronics.

[37]  M. Hegner,et al.  A multi-mode platform for cantilever arrays operated in liquid , 2013 .

[38]  Jelle E. Stumpel,et al.  Photoswitchable ratchet surface topographies based on self-protonating spiropyran-NIPAAM hydrogels. , 2014, ACS applied materials & interfaces.

[39]  Dermot Diamond,et al.  Spiropyran based hydrogels actuators - walking in the light , 2017 .

[40]  B. Feringa,et al.  UV/vis and NIR light-responsive spiropyran self-assembled monolayers. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[41]  U. Kolb,et al.  Ground- and First-Excited-Singlet-State Electric Dipole Moments of Some Photochromic Spirobenzopyrans in Their Spiropyran and Merocyanine Form † , 2002 .

[42]  Murali Krishna Ghatkesar,et al.  Processing of kinetic microarray signals , 2007 .

[43]  Thomas Thundat,et al.  Thermal and ambient-induced deflections of scanning force microscope cantilevers , 1994 .

[44]  H. Lang,et al.  Direct detection of a BRAF mutation in total RNA from melanoma cells using cantilever arrays. , 2013, Nature nanotechnology.

[45]  P. Théato,et al.  Light-induced wettability changes on polymer surfaces , 2014 .

[46]  H. Gruler,et al.  Reversible Photochemical Strain in Langmuir Monolayers , 1980 .

[47]  Jason Locklin,et al.  Fabrication of spiropyran-containing thin film sensors used for the simultaneous identification of multiple metal ions. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[48]  Mitchell T. Ong,et al.  Force-induced activation of covalent bonds in mechanoresponsive polymeric materials , 2009, Nature.

[49]  S. Cherian,et al.  Multiwell micromechanical cantilever array reader for biotechnology. , 2007, The Review of scientific instruments.

[50]  James K. Gimzewski,et al.  An artificial nose based on a micromechanical cantilever array , 1999 .

[51]  Photoinduced dilatational motion in monolayers of poly(methyl methacrylate) having benzospiropyran side groups , 1991 .

[52]  J. Fritz Cantilever biosensors. , 2008, The Analyst.

[53]  Libo Zhao,et al.  An immersive resonant sensor with microcantilever for pressure measurement , 2020 .