Fabrication and Elimination of PTAA/P4VP Layer-By-Layer Films

Layer-by-layer (LBL) ultra-thin films have been assembled by alternate adsorption of poly(3-thiophene acetic acid) (PTAA) and poly(4-vinylpyridine) (P4VP) on planar quartz slides via hydrogen-bonding interaction. Subsequently, the multilayers can be controllably removed by changing the pH values of the aqueous solutions used for film immersion. Our present study is an attempt to reveal the mechanisms of the multilayer film with two-dimensional (2D) ultraviolet-visible (UV-vis) correlation spectroscopy. UV-vis spectroscopy is primarily employed here to monitor the buildup and removal of the ultra-thin films. 2D correlation analysis is performed on the basis of the corresponding spectra for further studies. The morphology of the multilayer film is characterized by atomic force microscopy (AFM). When eliminated in alkaline and acidic aqueous solutions, the polymers in the films show diverse phenomena mainly due to the different extents of dissociation of PTAA and protonation of P4VP at different pH values. In alkaline solution, the elimination of PTAA takes place before P4VP, while in acid solution, the removal of these two polymers adopts a reverse order.

[1]  Gero Decher,et al.  Buildup of ultrathin multilayer films by a self‐assembly process, 1 consecutive adsorption of anionic and cationic bipolar amphiphiles on charged surfaces , 1991 .

[2]  Gero Decher,et al.  Multilayer Thin Films , 2002 .

[3]  Gero Decher,et al.  Polyelectrolytes I: Polyanion/Polycation Multilayers at the Air/Monolayer/Water Interface as Elements for Quantitative Polymer Adsorption Studies and Preparation of Hetero-superlattices on Solid Surfaces† , 2000 .

[4]  P. Bertrand,et al.  ToF-SIMS study of alternate polyelectrolyte thin films : Chemical surface characterization and molecular secondary ions sampling depth , 1996 .

[5]  Yoshihito Osada,et al.  Titration Behavior and Spectral Transitions of Water-Soluble Polythiophene Carboxylic Acids , 1999 .

[6]  M. Rubner,et al.  Micropatterning of polymer thin films with pH-sensitive and cross-linkable hydrogen-bonded polyelectrolyte multilayers. , 2002, Journal of the American Chemical Society.

[7]  M. Rubner,et al.  Novel Langmuir-Blodgett films of conducting polymers. 1. Polyion complexes and their multilayer heterostructures , 1992 .

[8]  J. Schlenoff,et al.  Polyelectrolyte Multilayers Containing a Weak Polyacid: Construction and Deconstruction , 2001 .

[9]  A. Goldstein,et al.  Modulation of protein adsorption and cell adhesion by poly(allylamine hydrochloride) heparin films. , 2005, Biomaterials.

[10]  V. Zucolotto,et al.  Dendrimers as nanoreactors to produce platinum nanoparticles embedded in layer-by-layer films for methanol-tolerant cathodes , 2006 .

[11]  Johannes Schmitt,et al.  Proof of multilayer structural organization in self-assembled polycation-polyanion molecular films , 1994 .

[12]  D. A. Korneev,et al.  Neutron reflectivity analysis of self-assembled film superlattices with alternate layers of deuterated and hydrogenated polysterenesulfonate and polyallylamine , 1995 .

[13]  A. Laschewsky,et al.  Bulk and Thin Films of Bismuth Vanadates Prepared from Hybrid Materials Made from an Organic Polymer and Inorganic Salts , 2006 .

[14]  I. Noda,et al.  Determination of Two-Dimensional Correlation Spectra Using the Hilbert Transform , 2000 .

[15]  Johannes Schmitt,et al.  Layer-by-layer assembled multicomposite films. , 1998 .

[16]  Changyou Gao,et al.  Stable microcapsules assembled stepwise from weak polyelectrolytes followed by thermal crosslinking , 2005 .

[17]  Young Mee Jung,et al.  Electrochemistry of conductive polymers. 34. Two-dimensional correlation analysis of real-time spectroelectrochemical data for aniline polymerization. , 2005, The journal of physical chemistry. B.

[18]  Xi Zhang,et al.  Multilayer Assemblies of Copolymer PSOH and PVP on the Basis of Hydrogen Bonding , 2000 .

[19]  S. Dubas,et al.  Mechanism of Polyelectrolyte Multilayer Growth: Charge Overcompensation and Distribution , 2001 .

[20]  E. Pereira,et al.  Luminescence of poly(3-thiopheneacetic acid) in alcohols and aqueous solutions of poly(vinyl alcohol) , 2001 .

[21]  T. Isaksson,et al.  Synchronicity and Linearity in Generalized Two-Dimensional Correlation Spectroscopy: Concepts Relevant to the Analysis of Nonperiodic, Monotonically Increasing or Decreasing Spectroscopic Signals , 2002 .

[22]  J. Schlenoff,et al.  Kinetics and multilayering in the adsorption of polyelectrolytes to a charged surface , 1996 .

[23]  G. J. Fleer,et al.  Formation and stability of multilayers of polyelectrolytes. , 1996 .

[24]  I. Noda Generalized Two-Dimensional Correlation Method Applicable to Infrared, Raman, and other Types of Spectroscopy , 1993 .

[25]  T. J. McCarthy,et al.  Stepwise Polymer Surface Modification: ChemistryLayer-by-Layer Deposition , 1998 .

[26]  M. Rubner,et al.  Molecular-Level Processing of Conjugated Polymers. 4. Layer-by-Layer Manipulation of Polyaniline via Hydrogen-Bonding Interactions , 1997 .

[27]  Xi Zhang,et al.  Investigation into an Alternating Multilayer Film of Poly(4-Vinylpyridine) and Poly(acrylic acid) Based on Hydrogen Bonding , 1999 .

[28]  J. Schlenoff,et al.  Multilayer Assemblies of Redox Polyelectrolytes , 1997 .

[29]  Xurong Xu,et al.  Stable superhydrophobic organic-inorganic hybrid films by electrostatic self-assembly. , 2005, The journal of physical chemistry. B.

[30]  Liao Wei,et al.  Monitoring Layer-by-layer Assembling of Films Containing Diazo-resines by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy , 2004 .

[31]  A. E. Dowrey,et al.  Generalized Two-Dimensional Correlation Spectroscopy , 2000 .

[32]  Carl A. Batt,et al.  Dendrimer-functionalized self-assembled monolayers as a surface plasmon resonance sensor surface. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[33]  J. Schlenoff,et al.  Multiple membranes from "true" polyelectrolyte multilayers. , 2001, Journal of the American Chemical Society.

[34]  Gero Decher,et al.  Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites , 1997 .

[35]  Y. Jung,et al.  Two-dimensional correlation analysis of spectroelectrochemical data for p-benzoquinone reduction in acetonitrile. , 2004, Analytical chemistry.

[36]  J. Lakowicz,et al.  A model for DNA detection by metal-enhanced fluorescence from immobilized silver nanoparticles on solid substrate. , 2006, The journal of physical chemistry. B.

[37]  P. Schaaf,et al.  In Situ Determination of the Structural Properties of Initially Deposited Polyelectrolyte Multilayers , 2000 .

[38]  Zhiqiang Wang,et al.  Hydrogen-Bonding-Directed Layer-by-Layer Multilayer Assembly: Reconformation Yielding Microporous Films , 2002 .

[39]  Frank Caruso,et al.  1. Ultrathin Multilayer Polyelectrolyte Films on Gold: Construction and Thickness Determination , 1997 .

[40]  Steve Granick,et al.  Layered, erasable polymer multilayers formed by hydrogen-bonded sequential self-assembly , 2002 .

[41]  S. Granick,et al.  Layered, Erasable, Ultrathin Polymer Films , 2000 .

[42]  J. Schlenoff,et al.  Charge and Mass Balance in Polyelectrolyte Multilayers , 1998 .

[43]  Johannes Schmitt,et al.  Internal structure of layer-by-layer adsorbed polyelectrolyte films : a neutron and X-ray reflectivity study , 1993 .