Gero Decher

The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes.

A new type of nanocellulosic material has been prepared by high-pressure homogenization of carboxymethylated cellulose fibers followed by ultrasonication and centrifugation. This material had a cylindrical cross-section as shown by transmission electron microscopy with a diameter of 5-15 nm and a length of up to 1 microm. Calculations, using the Poisson-Boltzmann equation, showed that the surface potential was between 200 and 250 mV, depending on the pH, the salt concentration, and the size of the fibrils. They also showed that the carboxyl groups on the surface of the nanofibrils are not fully dissociated until the pH has reached pH = approximately 10 in deionized water. Calculations of the interaction between the fibrils using the Derjaguin-Landau-Verwey-Overbeek theory and assuming a cylindrical geometry indicated that there is a large electrostatic repulsion between these fibrils, provided the carboxyl groups are dissociated. If the pH is too low and/or the salt concentration is too high, there will be a large attraction between the fibrils, leading to a rapid aggregation of the fibrils. It is also possible to form polyelectrolyte multilayers (PEMs) by combining different types of polyelectrolytes and microfibrillated cellulose (MFC). In this study, silicon oxide surfaces were first treated with cationic polyelectrolytes before the surfaces were exposed to MFC. The build-up of the layers was monitored with ellipsometry, and they show that it is possible to form very well-defined layers by combinations of MFC and different types of polyelectrolytes and different ionic strengths of the solutions during the adsorption of the polyelectrolyte. A polyelectrolyte with a three-dimensional structure leads to the build-up of thick layers of MFC, whereas the use of a highly charged linear polyelectrolyte leads to the formation of thinner layers of MFC. An increase in the salt concentration during the adsorption of the polyelectrolyte results in the formation of thicker layers of MFC, indicating that the structure of the adsorbed polyelectrolyte has a large influence on the formation of the MFC layer. The films of polyelectrolytes and MFC were so smooth and well-defined that they showed clearly different interference colors, depending on the film thickness. A comparison between the thickness of the films, as measured with ellipsometry, and the thickness estimated from their colors showed good agreement, assuming that the films consisted mainly of solid cellulose with a refractive index of 1.53. Carboxymethylated MFC is thus a new type of nanomaterial that can be combined with oppositely charged polyelectrolytes to form well-defined layers that may be used to form, for example, new types of sensor materials.

New nanocomposite films for biosensors: layer-by-layer adsorbed films of polyelectrolytes, proteins or DNA

Abstract This report describes the construction of ultrathin multicomponent films with an internal structure on the nanometre scale. In the simplest case, the films are built-up by the subsequent adsorption of polyanions and polycations. They can be fabricated on inorganic substrates such as glass, quartz or silicon wafers, or on various organic materials. The polymeric interlayers can incorporate materials with desired electrical or optical properties. The average thickness of the layers can be fine-tuned with Angstrom precision by the addition of suitable salts. They are temperature stable up to at least 200°C and can be laterally structured using conventional photolithographic techniques. The films provide for a well-defined substrate-independent interface for the immobilization of biological macromolecules, such as proteins or DNA, in their active state. The immobilization of streptavidin enables the controlled attachment of any biotinylated molecule with no resulting loss in its biological activity. Area-selective immobilization provides the possibility of built-in quality control for the fabrication of biosensors with separated reference and sample areas on the same substrate.

Layer-by-layer assembled multicomposite films

Three topics in the field of layer-by-layer assembly have made significant progress recently: structural investigations on multilayers composed of strong flexible polyelectrolytes and the development of a model for composition and architecture of films of this kind; the incorporation of enzymes in multilayers for either biosensing or multistep biocatalysis; and the investigation of electroluminescent properties of such films.

Functional core/shell nanoparticles via layer-by-layer assembly. investigation of the experimental parameters for controlling particle aggregation and for enhancing dispersion stability.

Gold nanoparticles (AuNPs) with a size of 13.5 nm were synthesized using well-established methods as described earlier by Turkevich (Turkevich, J.; Stevenson, P. C.; Hillier, J. Discuss. Faraday Soc. 1961, 11, 55-75) and Frens (Frens, G. Nature (London), Phys. Sci. 1973, 241, 20-22) using citrate as the reducing agent. It has already been reported that such AuNPs can easily be coated with polymeric shells using electrostatic layer-by-layer assembly of certain polyelectrolytes. Here, we show which parameters, namely, the polyelectrolyte concentration, the contour length of the polyelectrolyte chain, and the ionic strength, are preventing bridging flocculation during polyelectrolyte adsorption and enhancing the stability of the colloidal dispersion. For the preparation of individually coated particles with high yield, we identified optimal conditions such as the degree of polymerization of the polyelectrolytes used, the polyelectrolyte concentration, the nanoparticle concentration, and the concentration of added NaCl during multilayer buildup. Surprisingly, such functional nanoparticles are obtained with highest yield at a moderate excess of polyions. In contrast to expectations, a larger excess of polyions leads again to slight destabilization of the dispersion. The present findings raise our confidence to establish layer-by-layer deposition as a general method for functionalizing even different nanoparticles using a single method.

Assembly of polyelectrolyte multilayer films by consecutively alternating adsorption of polynucleotides and polycations

Abstract Multilayers films of nucleic acids (DNA, polyuridylic and polyadenylic acids) and polycations (polyallylamine, polyethylenimine, polylysine and polyarginine) were fabricated by consecutive adsorption of anionic and cationic polyelectrolytes. The film growth process was controlled by X-ray reflectivity and UV spectroscopy. The penetration of DNA-specific dye was examined for DNA-polyallylamine self-assembled films.

Determination of optical constants of molecular films assembled via alternate polyion adsorption

Abstract The optical properties of ordered multilayer assemblies produced by alternately dipping a substrate into polycation and polyanion solutions are investigated by using a planar optical waveguide as substrate and measuring the mode indices of the guided waves. The layers show a distinct positive birefringence, from which it is inferred that the polymer chains prefer to be oriented perpendicular to the interface (loops). If the films are equilibrated in water, the anistropy diminishes and the films are somewhat expanded. The kinetics of the assembly process was also studied by arranging for a flux of the polyion solution to pass over the waveguide surface while measuring the mode indices.

Protein adsorption onto auto-assembled polyelectrolyte films

Surface modification by deposition of ordered protein systems constitutes one of the major objectives of bio-related chemistry and biotechnology. In this respect a concept has recently been reported aimed at fabricating multilayers by the consecutive adsorption of positively and negatively charged polyelectrolytes. We investigate the adsorption processes between polyelectrolyte multilayers and a series of positively and negatively charged proteins. The film buildup and adsorption experiments were followed by Scanning Angle Reflectometry (SAR). We find that proteins strongly interact with the polyelectrolyte film whatever the sign of the charge of both the multilayer and the protein. When charges of the multilayer and the protein are similar, one usually observes the formation of protein monolayers, which can become dense. We also show that when the protein and the multilayer become oppositely charged, the adsorbed amounts are usually larger and the formation of thick protein layers extending up to several times the largest dimension of the protein can be observed. Our results confirm that electrostatic interactions dominate protein/polyelectrolyte multilayer interactions.

Neutron reflectivity analysis of self-assembled film superlattices with alternate layers of deuterated and hydrogenated polysterenesulfonate and polyallylamine

Abstract The neutron reflectivity pattern from a {PSS/PAH/PSS7d/PAH} × 8 thin film shows a well-shaped Bragg reflection (Q = 0.0063 A−1) and the Kiessig fringes (ΔQ = 0.0073 A−1) correspond to a spacing of 100 A and a total thickness of 850 A respectively.

Polyelectrolyte multilayers capped with polyelectrolytes bearing phosphorylcholine and triethylene glycol groups: parameters influencing antifouling properties.

In this paper, we investigate the design of antifouling surfaces by the deposition of polyelectrolytes modified by grafting of antifouling groups onto a (PSS/PAH)n precursor multilayer film [PSS, poly(styrenesulfonate); PAH, poly(allylamine)]. Different polyelectrolytes and different antifouling moieties are investigated, in particular, (EO)3 and (EO)3PC moieties (EO, ethylene oxide; PC, phosphorylcholine group). We find that protein adsorption can strongly be reduced and even practically suppressed through the deposition of only one layer of polyelectrolyte modified with PC and/or (EO)3 groups. We discuss the influence of various parameters such as the nature of the polyelectrolyte backbone, the nature of the antifouling moiety, and the grafting ratio on the reduction of protein adsorption. We find in particular that (EO)3 and (EO)3PC moieties grafted on poly(acrylic acid) (PAA) totally prevent protein adsorption for grafting ratios of 25% or more, at least within the detection limits of the used quartz crystal microbalance and optical waveguide light mode spectroscopy devices. The mechanism that leads to the antifouling property is discussed and compared to that leading to the antifouling properties of ethylene oxide self-assembled monolayers. Finally, by incorporating biotin on top of the precursor film, we show that one layer of PAA-(EO)3PC is not sufficient to prevent interaction with streptavidin but a PAA-(EO)3PC/PAH/PAA-(EO)3PC multilayer largely protects the biotin from interacting with streptavidin.

Bio-Inspired Multiproperty Materials: Strong, Self-Healing, and Transparent Artificial Wood Nanostructures

Nanocomposite films possessing multiple interesting properties (mechanical strength, optical transparency, self-healing, and partial biodegradability) are discussed. We used Layer-by-Layer assembly to prepare micron thick wood-inspired films from anionic nanofibrillated cellulose and cationic poly(vinyl amine). The film growth was carried out at different pH values to obtain films of different chemical composition, whereby, and as expected, higher pH values led to a higher polycation content and also to 6 times higher film growth increments (from 9 to 55 nm per layer pair). In the pH range from 8 to 11, micron thick and optically transparent LbL films are obtained by automated dipping when dried regularly in a stream of air. Films with a size of 10 cm(2) or more can be peeled from flat surfaces; they show tensile strengths up to about 250 MPa and Youngs moduli up to about 18 GPa as controlled by the polycation/polyanion ratio of the film. Experiments at different humidities revealed the plasticizing effect of water in the films and allowed reversible switching of their mechanical properties. Whereas dry films are strong and brittle (Youngs modulus: 16 GPa, strain at break: 1.7%), wet films are soft and ductile (Youngs modulus: 0.1 GPa, strain at break: 49%). Wet film surfaces even amalgamate upon contact to yield mechanically stable junctions. We attribute the switchability of the mechanical properties and the propensity for self-repair to changes in the polycation mobility that are brought about by the plastifying effect of water.