CO2-Responsive Polymer-Functionalized Au Nanoparticles for CO2 Sensor.

Metallic nanoparticles (NPs) coated with stimuli-responsive polymers (SRPs) exhibit tunable optical properties responding to external stimuli and show promising sensing applications. We present a new CO2-responsive polymer, poly(N-(3-amidino)-aniline) (PNAAN), coated gold NPs (AuNPs) synthesized by directly reducing HAuCl4 with a CO2-responsive monomer N-(3-amidino)-aniline (NAAN). The amidine group of PNAAN can be protonated into a hydrophilic amidinium group by dissolved CO2 (dCO2). This induces the PNAAN to swell and detach from the AuNP surface, resulting in AuNP aggregation and color change. By monitoring the UV absorbance change of AuNPs, a sensitive dCO2 sensor with a linear range of 0.0132 to 0.1584 hPa and a limit of detection (LOD) of 0.0024 hPa is developed. This method shows dramatic improvement in sensitivity and convenience of sample preparation compared with the previously reported dCO2 sensor.

[1]  Darrick J. Williams,et al.  Low-Temperature Synthesis of Au/Polyaniline Nanocomposites: Toward Controlled Size, Morphology, and Size Dispersity , 2012 .

[2]  Patrick Theato,et al.  CO2 -Responsive polymers. , 2013, Macromolecular rapid communications.

[3]  A. Müller,et al.  Amphiphilic Cylindrical Core−Shell Brushes via a “Grafting From” Process Using ATRP , 2001 .

[4]  Beat Müller,et al.  Fluorescence optical sensor for low concentrations of dissolved carbon dioxide , 1996 .

[5]  A. Müller,et al.  Superparamagnetic Hybrid Nanocylinders , 2004 .

[6]  L. Y. Yung,et al.  Synthesis of Self‐Stabilized Poly(N‐(3‐Amidino)‐Aniline) Particles and their CO2‐Responsive Properties , 2015 .

[7]  X. Liu,et al.  A Gold Nanoparticle‐Based Aptamer Target Binding Readout for ATP Assay , 2007 .

[8]  A. Metters,et al.  Synthetic matrix metalloproteinase-sensitive hydrogels for the conduction of tissue regeneration: Engineering cell-invasion characteristics , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[9]  Ying Ma,et al.  Formation and Self-assembly of Gold Nanoplates through an Interfacial Reaction for Surface-Enhanced Raman Scattering. , 2016, ACS applied materials & interfaces.

[10]  O. Wolfbeis,et al.  Surface plasmon resonance sensor for dissolved and gaseous carbon dioxide. , 2012, Analytical chemistry.

[11]  Kai Liu,et al.  pH and enzymatic double-stimuli responsive multi-compartment micelles from supra-amphiphilic polymers , 2012 .

[12]  Ying Ma,et al.  Detection of dissolved CO(2) based on the aggregation of gold nanoparticles. , 2014, Analytical chemistry.

[13]  Wenmiao Shu,et al.  Highly reversible and multi-stage cantilever actuation driven by polyelectrolyte brushes. , 2006, Journal of the American Chemical Society.

[14]  Jinying Yuan,et al.  CO2-responsive polymeric vesicles that breathe. , 2011, Angewandte Chemie.

[15]  Sarit S. Agasti,et al.  Gold nanoparticles in chemical and biological sensing. , 2012, Chemical reviews.

[16]  D. Fernig,et al.  Determination of size and concentration of gold nanoparticles from UV-vis spectra. , 2007, Analytical chemistry.

[17]  Jens Zosel,et al.  The measurement of dissolved and gaseous carbon dioxide concentration , 2011 .

[18]  T. Okano,et al.  Effects of graft densities and chain lengths on separation of bioactive compounds by nanolayered thermoresponsive polymer brush surfaces. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[19]  Evgeny Katz,et al.  Switchable selectivity for gating ion transport with mixed polyelectrolyte brushes: approaching ‘smart’ drug delivery systems , 2009, Nanotechnology.

[20]  T. Darwish,et al.  Spiropyran-amidine: a molecular canary for visual detection of carbon dioxide gas. , 2011, Chemistry.

[21]  O. Wolfbeis,et al.  Optical sensing scheme for carbon dioxide using a solvatochromic probe. , 2011, Analytical chemistry.

[22]  L. Andrew Lyon,et al.  Bioresponsive hydrogels for sensing applications , 2009 .

[23]  J. Dzubiella,et al.  Thermosensitive Au-PNIPA yolk-shell nanoparticles with tunable selectivity for catalysis. , 2012, Angewandte Chemie.

[24]  Wenmiao Shu,et al.  Polyelectrolyte brush amplified electroactuation of microcantilevers. , 2008, Nano letters.

[25]  L. Ionov,et al.  Stimuli-responsive command polymer surface for generation of protein gradients , 2009, Biointerphases.

[26]  Kinji Asaka,et al.  Preparation of Gold−Solid Polymer Electrolyte Composites As Electric Stimuli-Responsive Materials , 2000 .

[27]  Ying Ma,et al.  Facile synthesis of hierarchical gold nanostructures and their catalytic application , 2016, Nanotechnology.

[28]  Luis M Liz-Marzán,et al.  Au@pNIPAM colloids as molecular traps for surface-enhanced, spectroscopic, ultra-sensitive analysis. , 2009, Angewandte Chemie.

[29]  G. Schatz,et al.  Optical properties of responsive hybrid au@polymer nanoparticles. , 2012, ACS nano.

[30]  S. Asher,et al.  Fast responsive crystalline colloidal array photonic crystal glucose sensors. , 2006, Analytical chemistry.

[31]  R. Krishna,et al.  Polyamine-tethered porous polymer networks for carbon dioxide capture from flue gas. , 2012, Angewandte Chemie.

[32]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[33]  Zeev Rosenzweig,et al.  Development of an aggregation-based immunoassay for anti-protein A using gold nanoparticles. , 2002, Analytical chemistry.

[34]  J. Dzubiella,et al.  Fine-Tuning the Structure of Stimuli-Responsive Polymer Films by Hydrostatic Pressure and Temperature , 2013 .

[35]  Xin Wang,et al.  A CO2-responsive surface with an amidine-terminated self-assembled monolayer for stimuli-induced selective adsorption. , 2014, Chemical communications.