Polyelectrolyte multilayer film

In recent years, the measurement of thick adlayers has received an increasing interest in the field of so-called polyelectrolyte multilayer films. These films sometimes have a thickness of several micrometers. Such large thicknesses are obviously not easily monitored using conventional waveguide sensors because of the limited penetration depth into the adlayer. Simply, waveguide sensors loses their sensitivity when the adsorbed layer thickness exceeds 2 3 times the penetration depth of the evanescent field and cannot be used to monitor films thicker than 350 nm12. 

The inner structure of polyelectrolyte multilayer films has been studied by neutron and X-ray reflectivity experiments by intercalating deuterated PSS into a nondeut-erated PSS/PAH assembly [94, 99]. An important lesson from these experiments is that polyelectrolytes in PEMs do not present well-defined layers but are rather interpenetrated or fussy systems. As a consequence, polyelectrolyte chains deposited in an adsorption step are intertwined with those deposited in the three or four previous adsorption cycles. When polyelectrolyte mobility is increased by immersion in NaCl 0.8 M, the interpenetration increases with time as the system evolves towards a fully mixed state in order to maximize its entropy ]100]. From the point of view of redox PEMs, polyelectrolyte interpenetration is advantageous in the sense that two layers of a redox polyelectrolyte can be in electrochemical contact even if they are separated by one or more layers of an electroinactive poly ion. For example, electrical connectivity between a layer of a redox polymer and the electrode is maintained even when separated by up to 2.5 insulating bUayers [67, 101-103]. 

Nolle AJ, Rubner MF, Cohen RE (2005) Determining the Young s modulus of polyelectrolyte multilayer films via stress-induced mechanical buckling instabilities. Macromolecules 38 5367-5370... 

Keywords wrinkling Thin-film Elastomeric polymer Polydimethylsiloxane Patterns Deformation Surfaces Self-assembly Polyelectrolyte multilayer films Thin-films Polymer brushes Colloidal crystallization Mechanical-properties Assembled monolayers Buckling instability Elastomeric polymer Tobacco-mosaic-virus Soft lithography Arrays... 

We demonstrated how ordered lines of colloidal polystyrene particles can be achieved by a simple dip coating process [70], We used wrinkles produced via a stretch retraction process of a glassy polyelectrolyte multilayer film mounted on a PDMS substrate. Here, the template was dipped into a colloidal particle suspension with the orientation of the wrinkle s grooves with the withdrawing direction of dipping as the sketch in Fig. 11 indicates. 

Collagen, poly-L-lysine/serum proteins from cell culture medium Crosslinked polyacrylic acid/polyacrylamide multilayer films, PEG Coculture of rat adrenal medulla cells and mouse fibroblasts L929 Photopatteming of polyelectrolyte multilayer film 2009 [110]... 

Chien HW, Chang ZY, Tsai WB (2009) Spatial control of cellular adhesion using photo-crosslinked micropatterned polyelectrolyte multilayer films. Biomaterials 30(12) 2209-2218... 

Picart C (2008) Polyelectrolyte multilayer films from physico-chemical properties to the control of cellular processes. Curr Med Chem 17 685-697... 

Thomas B, Thomas C, Kefeng R et al (2009) Multiple functionalities of polyelectrolyte multilayer films new biomedical applications. Adv Mater 21 1-27... 

Schwinte P, Voegel J-C, Picart C et al (2001) Stabilizing effects of various polyelectrolyte multilayer films on the structure of adsorbed/embedded fibrinogen molecules an ATR-FTIR study. J Phys Chem B 15 11906-11916... 

Schneider A, Vodouhe C, Richert L et al (2007) Multifunctional polyelectrolyte multilayer films combining mechanical resistance, biodegradability, and bioactivity. Biomacromolecules 8 139-145... 

Vodouhe C, Le Guen E, Mendez Garza J et al (2006) Control of drug accessibility on functional polyelectrolyte multilayer films. Biomaterials 27 4149—4156... 

Volodkin D, Schaaf P, Mohwald H et al (2009) Effective embedding of liposomes into polyelectrolyte multilayered films. The relative importance of hpid-polyelectrolyte and interpolyelectrolyte interactions. Soft Matter 5 1394—1405... 

Burke SE, Barrett CJ (2004) pH-Dependent loading and release behavior of small hydrophihc molecules in weak polyelectrolyte multilayer films. Macromolecules 37 5375-5384... 

Ren K, Crouzier T, Roy C et al (2008) Polyelectrolyte multilayer films of controlled stiffness modulate myoblast cell differentiation. Adv Funct Mater 18 1-12... 

Richter L, Lavalle P, Vautier D et al (2002) Cell interactions with polyelectrolyte multilayer films. Biomacromolecules 3 1170-1178... 

Tryoen-Toth P, Vautier D, Haikel Y et al (2002) Viability, adhesion, and bone phenotype of osteoblast-like cells on polyelectrolyte multilayer films. J Biomed Mater Res 60 657-667... 

Hoshi, T., Saiki, H., Kuwazawa, S., Tsuchiya, C., Chen, Q., Anzai, J. (2001). Selective permeation of hydrogen peroxide through polyelectrolyte multilayer films and its use for amperometric biosensors, Chem. 73 5310-15. 

The first of our preliminary results we demonstrate here is mass sensitivity. To do this we use a polyelectrolyte multilayer layer-by-layer deposition technique. Briefly, multilayers of polyethyleneimine and polyacrylic acid were deposited on the glutaraldehyde functionalized NOSA device, and on similarly functionalized silicon wafers in parallel. After deposition of each layer, output spectra were recorded to quantify shift in resonant wavelengths and polyelectrolyte multilayer film thickness was determined on silicon wafers using ellipsometry. Output spectra were compared to the initial baseline spectra to determine resonance shift (AA, in mn), and were plotted against film thickness as shown in Fig. 2. 

Burchardt M, Wittstock G. Kinetic studies of glucose oxidase in polyelectrolyte multilayer films by means of scanning electrochemical microscopy (SECM). Bioelectrochem 2008 72 66-76. 

Soc., 1999, 121, 3435 T. Hoshi, H. Saiki, S. Kuwazawa, Y. Kobayama and A. Anzai, Polyelectrolyte multilayer film-coated electrodes for amperometric determination of hydrogen peroxide in the presence of ascorbic acid, uric acid and acetaminophen, Anal. Sci., 2000, 16, 1009 E.S. Forzani, VM. Solis and E.J. Calvo, Electrochemical behavior of polyphenol oxidase immobilized in self-assembled structures layer by layer with cationic polyallylamine, Anal. Chem., 2000, 72, 5300 Y.M. Lvov, Z. Lu, J.B. Schenkman, X. Zu and J.F. Rusling, Direct electrochemistry of myoglobin and cytochrome P450cam in alternate layer-by-layer film with DNA and other polyions, J. Am. Chem. Soc., 1998, 120, 4073. 

Bilayer films of poly(ethyleneimme) (positively charged) and poly(ethylene-co-maleic acid) have been used for chemical sensing [49]. The technique of surface plasmon resonance was used to monitor, in-situ, the deposition of these films. Subsequent exposure to aqueous solutions of metal acetate (metal = copper, nickel) resulted in a shift in position of the SPR curve. Phase-separated polyelectrolyte multilayer films that undergo a reversible pH-induced swelling transition have also been exploited for erasable nanoporous antireflection coatings, opening up applications for biore-sponsive materials and membrane applications [50]. 

Chung AJ, Rubner MF. 2002. Methods of loading and releasing low molecular weight cationic molecules in weak polyelectrolyte multilayer films. Langmuir 18(4) 1176 1183. 

Losche M, Schmitt J, Decher G, Bouwman WG, Kjaer K. 1998. Detailed structure of molecularly thin polyelectrolyte multilayer films on solid substrates as revealed by neutron reflectometry. Macromolecules 31(25) 8893 8906. 

McAloney RA, Dudnik V, Goh MC. 2003. Kinetics of salt induced annealing of a polyelectrolyte multilayer film morphology. Langmuir 19(9) 3947 3952. 

McAloney, R.A., Sinyor, M., Dudnik. V., Goh, M.C. Atomic force microscopy studies of salt effects on polyelectrolyte multilayer film morphology. Langmuir 2001,17 (21), 6655—6663. 

Caruso et al. [69] reported the preparation of negatively charged polystyrene latex particles (640 nm diameter) armored with a nanocomposite multilayer of Si02 nanoparticles (Ludox TM-40 26 4nm diameter) and poly(diallyldimethyl-ammonium chloride) (PDADMAC). These two components were sequentially adsorbed onto the surface of the polystyrene latex spheres (see Fig. 11), after adsorption of a precursor polyelectrolyte multilayer film of PDADMAC/... 

Sukhorukov GB, Mohwald H, Decher G, Lvov YM (1996) Assembly of polyelectrolyte multilayer films by consecutively alternating adsorption of polynucleotides and polycations. Thin Solid Films 284-285 220-223... 

In another study, Goncalves et al. showed a method to enhance stan cell recruitment by incorporation and release of stromal-derived factor 1 (SDFla) from self-assembled matrices composed of PGA and chitosan [282]. Chitosan and y-PGA, being oppositely charged, could self-assemble via electrostatic interactions to form stable surface coatings, such as polyelectrolyte multilayer films with thicknesses in the range of 120 nm. They showed the incorporation of... 

However, the fact that just within 4 years of the first report on polyelectrolyte multilayer films, homogeneous large area light emitting diodes have been described, has produced considerable enthusiasm towards applications (especially in the field of light emitting diodes) of these layered polymeric nanoheterostructures. 

Cutler, C.A., M. Bouguettaya, T.-S. Kang, and J.R. Reynolds. 2005. Alkoxysulfonate-functionalized PEDOT polyelectrolyte multilayer films Electrochromic and hole transport materials. Macromolecules 38 3068-3074. 

A final important motif for self-assembly of CPEs is by LbL deposition of polyelectrolyte multilayer films. The LbL multilayer film deposition method was first introduced by Decher [37,38], and since then it has been used to fabricate nanostructured films using a wide variety of synthetic and naturally occurring polyelectrolytes [39]. Deposition of LbL films involves a very simple sequence of alternately dipping a substrate into solutions that contain a cationic polyelectrolyte and an anionic polyelectrolyte. The sequential LbL deposition method leads to formation of polymer multilayer film structures. A single... 

FIGURE 5.18 Water chemical shift as a function of water content per ion pair for a five bilayer film. (Adapted with permission from McCormick, M., Smith, R.N., Graf, R., Barrett, C.J., Reven, L., and Spiess, H.W., NMR studies of the effect of adsorbed water on polyelectrolyte multilayer films in the solid state, Macromolecules 36, 3616-3625, 2003. Copyright 2003 American Chemical Society.)... 

MatsusaM, M., Sakaguchi, H., Serizawa, T., Akashi, M., 2007. Controlled release of vascular endothelial growth factor from alginate hydrogels nano-coated with polyelectrolyte multilayer films. Journal of Biomaterials Science Polymer Edition 18 (6), 775-783. 

Scheme 10.4 Mechanism of the glucose-induced decomplexation of a PBA-containing layer-by-layer assembled polyelectrolyte multilayer film. The green circles represent the uncharged PBA groups that become anionic (orange circles) after addition of glucose. (Reprinted with permission from ref. 99. Copyright 2006 American Chemical Society.)...

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