Layer-by-layer Technique Research Articles

Layer-by-layer assembled films of multi-walled carbon nanotubes with chitosan and cellulose nanocrystals

Chitosan solutions and cellulose nanocrystal suspensions were used to produce highly stable aqueous dispersions of multi-walled carbon nanotubes (MWCNTs). The different MWCNT dispersions, presenting positive and negative charges, were used to prepare multilayered hybrid thin films through electrostatic layer-by-layer (LBL) self-assembly. The MWCNTs are well dispersed and homogeneously distributed on each layer of chitosan and cellulose nanocrystals of the films. The nanotubes are densely packed in each multilayer, forming a random network. The surface of the LBL film exhibited a uniform and relatively smooth surface with a mean roughness value of ∼5.8±0.4nm. Electrochemical characterization revealed a decrease in two orders of magnitude in the film resistance as the number of bilayers increased from 5 to 20, which is a consequence of an increase in the amount of conductive material (MWCNT). The thin films with up to 20 bilayers exhibited transmittance higher than 90% in the visible range. The results presented in this work demonstrate the viability of the LBL technique for the deposition of active materials using the biopolymer pair chitosan/cellulose nanocrystals. The obtained films can be employed for the design of transparent and biocompatible carbon nanostructured based electrodes.

A new self-assembled layer-by-layer glucose biosensor based on chitosan biopolymer entrapped enzyme with nitrogen doped graphene

The layer-by-layer (LbL) technique has been used for the construction of a new enzyme biosensor. Multilayer films containing glucose oxidase, GOx, and nitrogen-doped graphene (NG) dispersed in the biocompatible positively-charged polymer chitosan (chit+(NG+GOx)), together with the negatively charged polymer poly(styrene sulfonate), PSS−, were assembled by alternately immersing a gold electrode substrate in chit+(NG+GOx) and PSS− solutions. Gravimetric monitoring during LbL assembly by an electrochemical quartz microbalance enabled investigation of the adsorption mechanism and deposited mass for each monolayer. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the LbL modified electrodes, in order to establish the contribution of each monolayer to the overall electrochemical properties of the biosensor. The importance of NG in the biosensor architecture was evaluated by undertaking a comparative study without NG in the chit layer. The GOx biosensor's analytical properties were evaluated by fixed potential chronoamperometry and compared with similar reported biosensors. The biosensor operates at a low potential of −0.2V vs., Ag/AgCl, exhibiting a high sensitivity of 10.5μAcm−2mM−1, and a detection limit of 64μM. This study shows a simple approach in developing new biosensor architectures, combining the advantages of nitrogen-doped graphene with the LbL technique for enzyme immobilization.

On the distinct molecular architectures of dipping- and spray-LbL films containing lipid vesicles

The introduction of spraying procedures to fabricate layer-by-layer (LbL) films has brought new possibilities for the control of molecular architectures and for making the LbL technique compliant with industrial processes. In this study we show that significantly distinct architectures are produced for dipping and spray-LbL films of the same components, which included DODAB/DPPG vesicles. The films differed notably in their thickness and stratified nature. The electrical response of the two types of films to aqueous solutions containing erythrosin was also different. With multidimensional projections we showed that the impedance for the DODAB/DPPG spray-LbL film is more sensitive to changes in concentration, being therefore more promising as sensing units. Furthermore, with surface-enhanced Raman scattering (SERS) we could ascribe the high sensitivity of the LbL films to adsorption of erythrosin.

Preparation of low-pressure water softening hollow fiber membranes by polyelectrolyte deposition with two bilayers

The layer-by-layer (LBL) polyelectrolyte deposition was applied on polyethersulfone (PES) hollow fiber ultrafiltration membrane to prepare nanofiltration (NF) membrane for low pressure water softening application for the first time. The effects of polyelectrolyte type and molecular weight (MW), deposited bilayer number, polyelectrolyte solution pH and supporting electrolyte concentration on the performance of resultant membranes were studied thoroughly.Experiments revealed that the pH of the polyelectrolyte solution and supporting electrolyte concentration presented the most notable effects. For weak poly-cations, Poly(ethylenimine) (PEI) and Poly(allylamine hydrochloride) (PAH), the solution pH affected the membrane performance significantly, and high water permeability and divalent cation rejection were obtained at optimum pH values. Using a low concentration of supporting electrolyte at underneath layers was proved to be an effective way to increase water permeability while maintaining high salt rejection. A salt water flux (SWP) of 12LMH/bar and 94% Mg2+ rejection was obtained by depositing only two bilayers of PSS/PAH polyelectrolytes on the PES substrate, while for the 3000ppm mixed salt solution, the water permeability was 11LMH/bar with Mg2+ and Ca2+ rejection as high as 90%. These promising results demonstrate that LBL technique is potentially applicable for preparing low-pressure water softening hollow fiber membranes.

Self-assembled hybrid nanoarchitectures deposited on poly(urethane) foams capable of chemically adapting to extreme heat

In the present paper the layer by layer (LbL) technique has been adopted for the construction of hybrid organic–inorganic nanoarchitectures capable of adapting to extreme heat or flame exposure and chemically evolving into thermally-stable carbon based structures. More specifically, the LbL technique has been applied to an open cell poly(urethane) (PU) foam in order to increase its thermal and flame stability. Scanning electron microscopy showed that the LbL assembly covered each surface of the PU complex three-dimensional structure without altering its open cell morphology. When exposed to a direct flame, the treated PU foam was capable of stopping combustion within a few seconds after ignition, unlike the untreated foam that burned completely. Under different irradiative heat fluxes (from 35 up to 75 kW m2), the coating demonstrated exceptional performances by reducing the rate of heat release up to 60% with respect to the untreated counterpart. Finally, when subjected to a flame torch penetration (Tflame ≈ 1300 °C), the LbL-coated PU foam was capable of maintaining its three-dimensional structure, thus successfully insulating the unexposed side (T below 100 °C after two flame torch applications) with temperature drops of 800 °C achieved with a specimen thickness of only 10 mm.

Characterization of casein and poly-l-arginine multilayer films

Thin films containing casein appear to be a promising material for coatings used in the medical area to promote biomineralization. α- and β-casein and poly-l-arginine multilayer films were formed by the layer-by layer technique and their thickness and mass were analyzed by ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D). (PLArg/casein) films deposited in 0.15M NaCl exhibit fast (exponential-like) growth of the film thickness with the number of layers. The resulting films were c.a. 10 times thicker than obtained for poly-l-arginine and natural polyanions. We investigated the effect of the type of casein used for the film formation, finding that films with α-casein were slightly thicker than ones with β-casein. The effect of polyethylene imine anchoring layer on the thickness and mass of adsorbed films was similar as for linear polyelectrolyte pairs. Thickness of “wet” films was c.a. two times larger than measured after drying that suggests their large hydration. The analysis of the mass of films during their post-treatment with the solutions of various ionic strength and pH provided the information concerning films stability. Films remain stable in the neutral and weakly basic conditions that includes HEPES buffer, which is widely used in cell culture and biomedical experiments. At the conditions of high ionic strength films swell but their swelling is reversible. Films containing caseins as polyanion appear to be more elastic and the same time more viscous than one formed with polyelectrolyte pairs. XPS elemental analysis confirmed binding of calcium ions by the casein embedded in the multilayers.

Recent progress in the applications of layer-by-layer assembly to the preparation of nanostructured ion-rejecting water purification membranes.

Reverse osmosis (RO) and nanofiltration (NF) are the two dominant membrane separation processes responsible for ion rejection. While RO is highly efficient in removal of ions it needs a high operating pressure and offers very low selectivity between ions. Nanofiltration on the other hand has a comparatively low operating pressure and most commercial membranes offer selectivity in terms of ion rejection. However in many nanofiltration operations rejection of monovalent ions is not appreciable. Therefore a high flux high rejection membrane is needed that can be applied to water purification systems. One such alternative is the usage of polyelectrolyte multilayer membranes that are prepared by the deposition of alternately charged polyelectrolytes via layer-by-layer (LbL) assembly method. LbL is one of the most common self-assembly techniques and finds application in various areas. It has a number of tunable parameters like deposition conditions, number of bilayers deposited etc. which can be manipulated as per the type of application. This technique can be applied to make a nanothin membrane skin which gives high rejection and at the same time allow a high water flux across it. Several research groups have applied this highly versatile technique to prepare membranes that can be employed for water purification. Some of these membranes have shown better performance than the commercial nanofiltration and reverse osmosis membranes. These membranes have the potential to be applied to various different aspects of water treatment like water softening, desalination and recovery of certain ions. Besides the conventional method of LbL technique other alternative methods have also been suggested that can make the technique fast, more efficient and thereby make it more commercially acceptable.

Anticorrosive ultrathin film derived from bio-based urushiol–Ti by layer-by-layer self-assembly

Abstract Urushiol–metal polymers, obtained by the reaction between metal and urushiol (an extraction of natural Chinese lacquer sap), are a heavy anticorrosive coating used in chemical industry because of their excellent resistance against chemical medias. Herein, through layer-by-layer (LBL) self-assembly of n-butyl titanate and urushiol, a stable anticorrosive multilayer inorganic–organic hybrid Ti/ polyurushiol (Ti/PU)n ultrathin film was constructed after UV irradiation. The formation of the (Ti/PU)n ultrathin film was monitored by Fourier transform infrared (FT-IR) spectroscopy and UV–vis spectroscopy, while the microstructure of the film was analyzed by X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XRR), atomic force microscopy (AFM) and scanning electron microscopy (SEM) . The anticorrosion property of the (Ti/U)n film with number n (n = 1, 3, 5, 7, 9, 11) and (Ti/PU)n (n = 3, 5, 7, 9, 11) film was investigated in concentrated salt aqueous solution using potentiodynamic polarization measurement. Due to the compact and defectless three-dimensional cross-linking network structure through the coordinate bonding between urushiol and Ti by LBL technique and subsequent photo-induced polymerization, the resultant (Ti/PU)7 film showed pronounced protective efficiency with inhibiting efficiency (IE) of greater than 99%. The morphology of (Ti/PU)7 film remained integrated and defect-free after immersion in 3.5 wt.% NaCl and 1 mol/L HCl solution for 24 h.

Photosystem II based multilayers obtained by electrostatic layer-by-layer assembly on quartz substrates

Photosystem II (PSII) proteins from spinach leaves were immobilized onto quartz substrates according to the Layer-by-Layer (LbL) procedure, alternating protein to polyethylenimine (PEI) layers by exploiting electrostatic interactions. The effects of several factors, such as storage conditions, ageing of the PSII-modified substrates, as well as PSII concentration in buffer, on the quality of the prepared multilayers, were investigated by UV-vis Absorption Spectroscopy and Atomic Force Microscopy (AFM). A number of 13 layers was found to be optimal to guarantee intense PSII optical signals with homogeneous morphological distributions of proteins. The multilayers resulted stable if stored in contact with air at 4 °C, as observed by UV-vis Absorption spectra recorded after 48 h. The best results in terms of AFM images and electron transfer efficiency (measured by Hill Reaction assays) were gained by using 5.6 × 10(-7) M chlorophyll concentration, obtaining multilayers with the most ordered protein distributions and the highest electron transfer efficiency, i.e. 85% of an iso-absorbing PSII suspension. The results highlight the possibility to successfully immobilize PSII proteins, without considerable loss of bioactivity, thanks to the mild nature of the electrostatic LbL technique, opening up possibilities of applications in the bioelectrochemical energy conversion and biosensoristic fields.

25th Anniversary Article: What Can Be Done with the Langmuir‐Blodgett Method? Recent Developments and its Critical Role in Materials Science

The Langmuir-Blodgett (LB) technique is known as an elegant method for fabrication of well-defined layered structures with molecular level precision. Since its discovery the LB method has made an indispensable contribution to surface science, physical chemistry, materials chemistry and nanotechnology. However, recent trends in research might suggest the decline of the LB method as alternate methods for film fabrication such as layer-by-layer (LbL) assembly have emerged. Is LB film technology obsolete? This review is presented in order to challenge this preposterous question. In this review, we summarize recent research on LB and related methods including (i) advanced design for LB films, (ii) LB film as a medium for supramolecular chemistry, (iii) LB technique for nanofabrication and (iv) LB involving advanced nanomaterials. Finally, a comparison between LB and LbL techniques is made. The latter reveals the crucial role played by LB techniques in basic surface science, current advanced material sciences and nanotechnologies.

Layer-by-Layer Enabled Nanomaterials for Chemical Sensing and Energy Conversion

The layer-by-layer (LbL) technique is a wet chemical method for the assembly of ultrathin films, with thicknesses up to 100 nm. This method is based on the successive transfer of molecular layers to a solid substrate that is dipped into cationic and anionic solutions in an alternating fashion. The adsorption is mainly driven by electrostatic interactions so that many molecular and nanomaterial systems can be engineered under this method. Moreover, it is inexpensive, can be easily performed, and does not demand sophisticated equipment or clean rooms. The most explored use of the LbL technique is to build up molecular devices for chemical sensing and energy conversion. Both applications require ultrathin films where specific elements must be organized with high control of thickness and spatial distribution, preferably in the nanolength and mesolength scales. In chemical sensors, the LbL technique is employed to assemble specific sensoactive materials such as conjugated polymers, enzymes, and immunological elements onto appropriated electrodes. Molecular recognition events are thus transduced by the assembled sensoactive layer. In energy-conversion devices, the LbL technique can be employed to fabricate different device’s parts including electrodes, active layers, and auxiliary layers. In both applications, the devices’ performance can be fully modulated and improved by simply varying film thickness and molecular architecture. The present review article highlights the main features of the LbL technique and provides a brief description of different (bio)chemical sensors, solar cells, and organic light-emitting diodes enabled by the LbL approach.

Bioactive coronary stent coating based on layer-by-layer technology for siRNA release

One procedure to treat stenotic coronary arteries is the percutaneous transluminal coronary angioplasty (PTCA). In recent years, drug-eluting stents (DESs) have demonstrated elaborate ways to improve outcomes of intravascular interventions. To enhance DESs, the idea has evolved to design stents that elute specific small interfering RNA (siRNA) for better vascular wall regeneration. Layer-by-layer (LbL) technology offers the possibility of incorporating siRNA nanoplexes (NPs) to achieve bioactive medical implant coatings. The LbL technique was used to achieve hyaluronic acid/chitosan (HA/Chi) films with incorporated Chi-siRNA NPs. The multilayer growth was monitored by quartz crystal microbalance. The coating on the stents and its thickness were analyzed using fluorescence and scanning electron microscopy. All stents showed a homogeneous coating, and the polyelectrolyte multilayers (PEMs) were not disrupted after ethylene oxide sterilization or expansion. The in vitro uptake of fluorescent-labeled NPs from PEMs in primary human endothelial cells (ECs) was analyzed by flow cytometry for 2, 6 and 9days. Furthermore, stents coated with HA/Chi and Chi-siRNA NPs were expanded into porcine arteries and showed ex vivo delivery of NPs. The films showed no critical results in terms of hemocompatibility. This study demonstrates that Chi-siRNA NPs can be incorporated into PEMs consisting of HA and Chi. We conclude that the NPs were delivered to ECs under in vitro conditions. Furthermore, under ex vivo conditions, NPs were transferred into porcine artery walls. Due to their good hemocompatibility, they might make an innovative tool for achieving bioactive coatings for coronary stents.

ChemInform Abstract: Layer‐by‐Layer Assembly of Microcapsules and Their Biomedical Applications

AbstractReview: 306 refs.

Toward More Efficient Bioelectrocatalytic Oxidation of Ethanol for Amperometric Sensing and Biofuel Cell Technology

The integrated, structured, and multifunctional bioelectrocatalytic system for effective oxidation of ethanol is developed here. The concept is based on the layer-by-layer (LbL) assembly through electrostatic attraction of positively charged, multiwalled carbon nanotubes and the controlled combination of dehydrogenase enzymes. More specifically, the LbL technique was employed for sequential immobilization of two dehydrogenase enzymes and poly(diallyldimethylammonium chloride)-covered multiwalled carbon nanotubes onto a glassy carbon electrode substrate. Both monoenzymatic [utilizing a single enzyme, alcohol dehydrogenase (ADH)] and bienzymatic (anchoring sequentially both ADH and aldehyde dehydrogenase) systems were tested. Multilayers were characterized using scanning electron microscopy, infrared spectroscopy, and cyclic voltammetry. The results are consistent with the view that our approach enables good control of distribution and efficient utilization of both enzymes within the biocomposite film and leads to sizable enhancement of the oxidation of ethanol through significant (more than 2-fold) increase of bioelectrocatalytic currents and by shifting the ethanol oxidation potential to 0.1 V (vs Ag/AgCl) or decreasing the overvoltage by ca. 200 mV in comparison with the monoenzymatic electrode system. This simple biocomposite (enzyme-cascade) system permits fabrication of highly sensitive ethanol biosensors based on nicotinamide adenine dinucleotide coenzyme-dependent dehydrogenases. Our ethanol biosensor exhibited a good linearity ranging from 50 to 300 μM, and it was characterized by a high sensitivity of 118.8 μA mM(-1) cm(-2) as well as a low detection limit of 24 μM.

Surface induced porous morphological transition of the organic self-assembled monolayer hybridized polyelectrolyte thin films

Surface coating is used for materials to achieve a desired surface property without changing the whole material. Polyelectrolyte multilayer (PEM) deposition may be one of the most versatile techniques to create conformal surface coating in large area with a great control over the film thickness in nano-meter scale. These multilayer films are assembled through, so called, the layer-by-layer (LbL) deposition process which is the repetitive, sequential dipping of the substrate into the oppositely charged polyelectrolytes solutions. PEM films can be used for various substrates (glass slides, silicon wafer, plastics, etc.) without any difficult treatment. Moreover, the functional groups which remained reactive after the film deposition allow further chemical reactions such as the polymer micro-contact printing and the selective crosslinking. Due to these advantages, many studies using the LbL technique have conducted intensively to create functional coatings for electro-optical and biomedical applications. Other frequently used method of surface coating is self-assembled monolayer (SAM) formation. SAM can form organic interfaces with the properties largely controlled by the end groups of the molecules comprising of the film. Certainly, these two methods are the most competitive fabrication techniques of surface coating. While the surface properties of most SAMs are presented by the nature of the end groups of SAM molecules, PEM films exhibit their surface properties that are orchestrated by the chemical compositions of the polyelectrolyte film and physical factors such as surface morphology, thickness, etc.. If these two very different materials meet, what phenomena will occur at the interface? How would they compensate their discrepancy? In this paper, we present a study of the coating system that was fabricated as a mixture of PEM and SAM. The hybrid films were prepared by polyelectrolyte multilayers comprised of hydrophilic polyelectrolytes assembled atop of hydrophobic SAM films. We have observed a unique phase separation of the SAM/PEM hybrid film, which lead the formation of nano-pores of the film surface. Surface properties including wetting and biological interaction behaviors of the hybrid films are also discussed in this paper.

Carbon nanotube-incorporated multilayered cellulose acetate nanofibers for tissue engineering applications

We report the fabrication of a novel carbon nanotube-containing nanofibrous polysaccharide scaffolding material via the combination of electrospinning and layer-by-layer (LbL) self-assembly techniques for tissue engineering applications. In this approach, electrospun cellulose acetate (CA) nanofibers were assembled with positively charged chitosan (CS) and negatively charged multiwalled carbon nanotubes (MWCNTs) or sodium alginate (ALG) via a LbL technique. We show that the 3-dimensional fibrous structures of the CA nanofibers do not appreciably change after the multilayered assembly process except that the surface of the fibers became much rougher than that before assembly. The incorporation of MWCNTs in the multilayered CA fibrous scaffolds tends to endow the fibers with improved mechanical property and promote fibroblast attachment, spreading, and proliferation when compared with CS/ALG multilayer-assembled fibrous scaffolds. The approach to engineering the nanofiber surfaces via LbL assembly likely provides many opportunities for new scaffolding materials design in various tissue engineering applications.

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

The intensive research of the optical properties of rare-earth ions is due to the high quantum efficiency of their emission, very narrow bands, and excellent fluorescence monochromaticity. The photoluminescence data presented here show that the nanophosphor remains a green emitter in Layer-by-Layer (LbL) films leading to potential application in optical devices or biological labeling. The LbL technique, an established method for thin film fabrication with molecular architecture control, is used in the manufacture of a hybrid film containing the cationic polyelectrolyte poly (allylamine hydrochloride) (PAH) and Y2O3: Er, Yb nanophosphor. The spectroscopic properties of this luminescent nanomaterial are extracted from the spectral data of the powder, cast film and LbL films. The growth of the LbL film was monitored by absorbance versus concentration plots in ultraviolet–visible (UV–Vis) absorption spectroscopy. The presence of both PAH and nanophosphor in the LbL film was confirmed by Fourier transform infrared (FTIR) absorption spectroscopy. The FTIR data also ruled out the existence of chemical interactions between the PAH and nanophosphor layers, which means that secondary interactions (like Van der Waals forces) might be the driving forces for LbL film growth. The morphology and the spatial distribution of the LbL film components along the film surface were probed with micrometer spatial resolution combining optical microscopy and Raman mapping. In addition, the observation of intense electronic emission lines from doping ions showed micro-spectroscopy as a highly sensitive analytical technique for characterization of films containing nanophosphors.

Characterization and cell behavior of titanium surfaces with PLL/DNA modification via a layer‐by‐layer technique

This study describes the fabrication of two types of multilayered films onto titanium by layer-by-layer (LBL) self-assembly, using poly-L-lysine (PLL) as the cationic polyelectrolyte and deoxyribonucleic acid (DNA) as the anionic polyelectrolyte. The assembling process of each component was studied using atomic force microscopy (AFM) and quartz crystal balance (QCM). Zeta potential of the LBL-coated microparticles was measured by dynamic light scattering. Titanium substrates with or without multilayered films were used in osteoblast cell culture experiments to study cell proliferation, viability, differentiation, and morphology. Results of AFM and QCM indicated the progressive build-up of the multilayered coatings. The surface morphology of three types of multilayered films showed elevations in the nanoscale range. The data of zeta potential showed that the surface terminated with PLL displayed positive charge while the surface terminated with DNA displayed negative charge. The proliferation of osteoblasts on modified titanium films was found to be greater than that on control (p < 0.05) after 3 and 7 days culture, respectively. Alamar blue measurement showed that the PLL/DNA-modified films have higher cell viability (p < 0.05) than the control. Still, the alkaline phosphatase activity assay revealed a better differentiated phenotype on three types of multilayered surfaces compared to noncoated controls. Collectively our results suggest that PLL/DNA were successfully used to surface engineer titanium via LBL technique, and enhanced its cell biocompatibility.

Optical fibre long period grating with a nanoporous coating formed from silica nanoparticles for ammonia sensing in water

A fibre optic long period grating (LPG) with an nano-assembled mesoporous coating of alternate layers of poly(diallyldimethylammonium chloride) (PDDA) and SiO2 nanospheres was used for the development of a highly sensitive fibre-optic chemical sensor. Sensor fabrication involves a 2-stage process: firstly, the deposition of the base mesoporous thin film (PDDA/SiO2) over an LPG written in the optical fibre using a layer-by layer technique, followed by the infusion of a functional material into the porous film. The refractive index of the base mesoporous coating, determined at a wavelength of 633nm using ellipsometry, was found to be 1.2. The infusion of the functional material into the coating resulted in a significant change in the RI of the coating, producing a dramatic change in the transmission spectrum of the LPG. The sensing mechanism exploited is based upon chemically induced desorption of the functional material from the mesoporous coating. The sensing of ammonia in aqueous solution was chosen as an example to demonstrate the sensing principle of the LPG sensor. The operation of the sensor was characterized using two functional materials, tetrakis-(4-sulfophenyl)porphine (TSPP) and polyacrylic acid (PAA). The device showed high sensitivity to ammonia with a response time less than 100s and a limit of detection of 140ppb when the TSPP infused (PDDA/SiO2) film was employed as a sensitive element.

Natural rubber latex LbL films: Characterization and growth of fibroblasts

AbstractThe recent biomedical applications of natural rubber (NR) latex, mostly in dry membranes, have motivated research into novel, more noble uses of this low‐cost biomaterial. In this article, we provide the first report on the fabrication of layer‐by‐layer (LbL) films of NR alternated with the polyelectrolytes polyethylenimine (PEI) and polyallylamine hydrochloride (PAH). Stable (PAH/NR)n and (PEI/NR)n LbL films displayed similar physicochemical properties, but differed in terms of film morphology according to atomic force microscopy (AFM) and scanning electron microscopy (SEM) data. Most significantly, (PEI/NR)5 LbL films were made of smaller and flattened particles, which were not efficient for the growth and proliferation of normal human fibroblasts (NHF). In contrast, efficient NHF proliferation could be obtained with (PAH/NR)n LbL films, with the fibroblasts exhibiting the expected elongated morphology. Furthermore, cell growth did not occur for cast films of NR, thus demonstrating the suitability of the LbL method for this biologically related application. The differences between the two polyelectrolytes illustrate the importance of the film architecture and morphology, which open the way for exploiting the molecular control inherent in the LbL technique for further applications of NR‐containing films. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012