Free-standing Multilayer Films Research Articles

Free-standing multilayer films as growth factor reservoirs for future wound dressing applications

Chronic skin wounds place a high burden on patients and health care systems. The use of angiogenic and mitogenic growth factors can facilitate the healing but growth factors are quickly inactivated by the wound environment if added exogenously. Here, free-standing multilayer films (FSF) are fabricated from chitosan and alginate as opposing polyelectrolytes in an alternating manner using layer-by-layer technique. One hundred bilayers form an about 450 μm thick, detachable free-standing film that is subsequently crosslinked by either ethyl (dimethylaminopropyl) carbodiimide combined with N-hydroxysuccinimide (E-FSF) or genipin (G-FSF). The characterization of swelling, oxygen permeability and crosslinking density shows reduced swelling and oxygen permeability for both crosslinked films compared to non-crosslinked films (N-FSF). Loading of fibroblast growth factor 2 (FGF2) into the films results in a sustained release from crosslinked FSF in comparison to non-crosslinked FSF. Biocompatibility studies in vitro with human dermal fibroblasts cultured underneath the films demonstrate increased cell growth and cell migration for all films with and without FGF2. Especially G-FSF loaded with FGF2 greatly increases cell proliferation and migration. In vivo biocompatibility studies by subcutaneous implantation in mice show that E-FSF causes an inflammatory tissue response that is absent in the case of G-FSF. N-FSF also represents a biocompatible film but shows early degradation. All FSF possess antibacterial properties against gram+ and gram- bacteria demonstrated by an agar diffusion disc assay. In summary, FSF made of alginate and chitosan crosslinked with genipin can act as a reservoir for the sustained release of FGF2, possessing high biocompatibility in vitro and in vivo. Moreover, G-FSF promotes growth and migration of human dermal fibroblasts and has antibacterial properties, which makes it an interesting candidate for bioactive wound.

Charge-switchable, anti-oxidative molecule tuned polyelectrolyte multilayered films: Amplified polyelectrolyte diffusivity and accelerated diabetes wound healing

The local oxidizing microenvironment and bacterial infection, as crucial internal and external factors that hinder the healing of diabetic wounds, are two main issues to be addressed in the design of novel wound dressing materials. As an attempt to provide optimal solution to the aforementioned problems, free-standing (FS) polyelectrolyte multilayer films (PEMs) loaded with bis[2-(4-hydroxyphenyl) benzimidazole] (BHPB) were constructed by layer-by-layer (LBL) self-assembly method. The exponential growth of LBL deposition as well as the film degradation were extensively studied, our results revealed that by pre-assembling polycation with the pH-sensitive BHPB molecule, the polycation diffusivity was largely accelerated thus greatly amplified LBL film growth, ensuring the facile detachment of the PEMs from the substrates to achieve FS films. The increase in BHPB content leaded to faster film growth and slower film degradation and more sustainable BHPB release. In terms of multifunctionality, which was ideal for the design of wound dressing material, the obtained FS films exhibited effective antimicrobial and antioxidant properties thanks to the addition of bioactive BHPB. Notably, unlike traditional antioxidant materials that only neutralize reactive oxygen species (ROS), the BHPB-loaded films stimulated the Kelch-like ECH-associated protein 1 (Keap1)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) axis, which is a vital intercellular ROS scavenging system blocked by hyperglycemia. Moreover, the wound treated by BHPB-incorporated PEMs exhibited faster healing with increased collagen deposition, enhanced angiogenesis, and rapid re-epithelialization in rat diabetic cutaneous defect models. Overall, in the perspective of cost-effectiveness and simple fabrication, the composite BHPB incorporated FS films reported in the current study showed rather promising potential in the application of diabetic wound healing.

Improving shape memory alloys for solid-state cooling

The freestanding multilayer thin films fabricated by sputtering deposition can withstand more than 20 million cycles.

A free-standing multilayer film as a novel delivery carrier of platelet lysates for potential wound-dressing applications

Great efforts have been made to develop suitable bioactive constructs that release growth factors (GFs) in a controlled manner for tissue-regeneration applications. Platelet lysates (PLs) are an affordable source of multiple GFs and other proteins, and show great potential in the wound-healing process. Herein, poly-l-lysine (PLL) and hyaluronic acid (HA) were applied to build free-standing polyelectrolyte multilayer films (PEMs) using the PH-amplified layer-by-layer self-assembly method. Molecular simulations were performed, which showed that in the end layer of PEMs, HA was more attractive to PLs than was PLL. The HA/PLL films constructed with or without 1-ethyl-3-[3-dimethylaminopropyl] carbodiimide hydrochloride (EDC) cross-linking both absorbed PLs successfully, exhibiting high hydrophilicity and GF absorptivity. The release profile of the EDC30 film lasted up to 2 weeks, and PL-loaded films supported cell proliferation, adhesion, migration, and angiogenesis in vitro. Moreover, due to sustained delivery of PLs, the membranes (especially the crosslinked film) helped to promote granulation-tissue formation, collagen deposition, and neovascularization in the region of the defect, resulting in rapid re-epithelialization and regeneration of skin. Mechanistically, the beneficial effects of a PL-loaded PEM coating might be related to activation of the hypoxia-inducible factor-1(Hif-1α)/vascular endothelial growth factor (VEGF) axis. As an off-the-shelf and cell-free treatment option, these biomimetic multilayers have great potential for use in the fabrication of devices that allow stable incorporation of PLs, thereby exerting synergistic effects for efficient wound healing.

Biocompatible, transparent, and water-resistant adhesive films with high mechanical stability derived from post-facile chemical cross-linking

Transparent surgical adhesives with excellent underwater adhesion and mechanical strength are strongly desirable for various biomedical applications such as wound closure and tissue healing. This is addressed in the present work by the development of biocompatible, transparent, and water-resistant adhesive films prepared from catechol-modified ε-poly(ʟ-lysine) and dopamine hydrochloride modified sodium hyaluronate layers successively applied using the layer-by-layer (LbL) assembly method. The LbL-assembled films are easily released from substrates via a mechanical exfoliation method with a blade to obtain free-standing multilayer films. The exceptional wet adhesion properties of the catechol groups yield films with excellent underwater adhesion strength. The underwater stability and mechanical strength of the free-standing multilayer films are improved via post-facile chemical cross-linking using biocompatible N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride. The post-treated free-standing multilayer films achieve a tensile strength of 0.36 ± 0.20 MPa and an elongation at break of 180.05% in water. The free-standing multilayer films exhibit a high optical transmittance greater than 55% in the visible region.

Self-Assembly of Metal-Organic Framework (MOF) Nanoparticle Monolayers and Free-Standing Multilayers.

We report the first self-assembled porous monolayer and free-standing multilayer films composed of metal-organic framework (MOF) nanoparticles. Self-assembled MOF monolayers (SAMMs) were assembled at a liquid-air interface to produce films that are 87 wt % (89 vol %) MOF. Monolayer self-assembly was aided by growing a layer of poly(methyl methacrylate) (PMMA) on the particle surface using a histamine anchor. SAMMs could be stacked to obtain MOF multilayers, including alternating MOF/polymer heterostructures. SAMMs were coated on silicon microparticles, and a MOF film constructed of only five stacked layers could be manipulated as a free-standing, opalescent film. These monolayers are a significant advancement for obtaining highly functional porous membranes and coatings.

Effect of Different Crosslinking Strategies on Physical Properties and Biocompatibility of Freestanding Multilayer Films Made of Alginate and Chitosan.

Freestanding multilayer films prepared by layer-by-layer technique have attracted interest as promising materials for wound dressings. The goal is to fabricate freestanding films using chitosan (CHI) and alginate (ALG) including subsequent crosslinking to improve the mechanical properties of films while maintaining their biocompatibility. Three crosslinking strategies are investigated, namely use of calcium ions for crosslinking ALG, 1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide combined with N-hydroxysuccinimide for crosslinking ALG with CHI, and Genipin for crosslinking chitosan inside the films. Different characteristics, such as surface morphology, wettability, swelling, roughness, and mechanical properties are investigated showing that films became thinner, exhibited rougher surfaces, had lower water uptake, and increased mechanical strength after crosslinking. Changes of wettability are moderate and dependent on the crosslinking method. In vitro cytotoxicity and cell attachment studies with human dermal fibroblasts show that freestanding CHI-ALG films represent a poorly adhesive substratum for fibroblasts, while studies using incubation of plastic-adherent fibroblast beneath floating films show no signs of cytotoxicity in a time frame of 7 days. Results from cell experiments combined with film characteristics after crosslinking, indicate that crosslinked freestanding films made of ALG and CHI may be interesting candidates for wound dressings.

The free-standing multilayer thick films of 0.7Pb(Zr0.46Ti0.54)O3–0.1Pb(Zn1/3Nb2/3)O3–0.2Pb(Ni1/3Nb2/3)O3 with low co-fired temperature

High performance free-standing multilayer PNN–PZN–PZT thick films have been successfully fabricated by tape-casting and one step co-fired method. Optimal formulation of slurries has been found. Free-standing multilayer thick films with Ag electrodes were obtained after co-fired at 900 °C. With proper pretreatment, compact structure and well combined PZT layers can be obtained, which indicates the tightly integrated structure of multilayer thick films. Diffusion and permeation between Ag electrodes and PZT layers was not observed in specimens sintered at 900 °C. The influences of organic content and sintering temperature on density and crystallinity were discussed. Nine layered specimens showed great electrical properties: d33, tanδ, e33 T /e0, g33 and Pr of 1880 pC N−1, 2.3%, 1067, 199.00 mV m/N, 82.77 µC cm−2. The displacement of nine layers specimens under same applied voltage was increased from 901 to 8489 nm compared with bulk ceramics. Those outstanding properties indicate that co-fired free-standing PNN–PZN–PZT multilayer thick films are suitable for application in MEMS system, energy harvesting device and piezoelectric power generation.

Adhesive free-standing multilayer films containing sulfated levan for biomedical applications

This work is the first reporting the use of layer-by-layer to produce adhesive free-standing (FS) films fully produced using natural-based macromolecules: chitosan (CHI), alginate (ALG) and sulfated levan (L-S). The deposition conditions of the natural polymers were studied through zeta potential measurements and quartz crystal microbalance with dissipation monitoring analysis. The properties of the FS films were evaluated and compared with the control ones composed of only CHI and ALG in order to assess the influence of levan polysaccharide introduced in the multilayers. Tensile tests, dynamic mechanical analysis and single lap shear strength tests were performed to evaluate the mechanical properties of the prepared FS films. The presence of L-S conferred both higher tensile strength and shear strength to the developed FS membranes. The results showed an adhesion strength 4 times higher than the control (CHI/ALG) FS films demonstrating the adhesive character of the FS films containing L-S. Morphological and topography studies were carried out revealing that the crosslinking reaction granted the L-S based FS film with a higher roughness and surface homogeneity. Preliminary biological assays were performed by cultivating myoblasts cells on the surface of the produced FS films. Both crosslinked and uncrosslinked FS films containing L-S were cytocompatible and myoconductive. Statement of SignificanceSutures remain as the “gold standard” for wound closure and bleeding control; however they still have limitations such as, high infection rate, inconvenience in handling, and concern over possible transmission of blood-borne disease through the use of needles. One of the challenges of tissue engineering consist on the design and development of biocompatible tissue adhesives and sealants with high adhesion properties to repair or attach devices to tissues. In this work, the introduction of sulfated levan (L-S) on multilayered free-standing membranes was proposed to confer adhesive properties. Moreover, the films were myoconductive even in the absence of crosslinking just by the presence of L-S. This study provides a promising strategy to develop biological adhesives and for cardiac tissue engineering applications.

Silver Nanoparticles Reinforced (Poly-(l-lysine)/Hyaluronic Acid) Free-Standing Films: The Mechanical Strength and Antibacterial Activity.

Free-standing polyelectrolyte multilayer films which are composed of biomacromolecules, such as polysaccharides and/or polypeptides, have attracted numerous attentions in biomedical fields. However, the poor mechanical strength makes their future applications difficult. In the present work, we used the pH-amplified Poly-(l-lysine)/Hyaluronic acid (PLL/HA) film as the template and in situ synthesized silver nanoparticles (AgNPs) in a green way. It was confirmed that the size of AgNPs in the films was largely dependent on the loading method of Ag+ (pre-complex vs. post-loading). Meanwhile, the loading amount of AgNPs and their distribution in the films could be controlled by the films outermost layer (PLL vs. HA) as observed under electron microscopies. The reduced AgNPs were used here as both bactericidal agent and mechanical reinforcer. The anti-bacterial activity of the films with AgNPs was verified by the Kirby-Bauer assay, and film cytotoxicity was examined by MTT examination. The effects of AgNPs' amount, size and distribution on the mechanical properties of films were evaluated by both nanoindentation and micro tensile tests. The films embedded with AgNPs of smaller size and well-distribution throughout the films gained the maximal enhancement on mechanical strength and preserved acceptable cytocompatibility. The in situ UV reduction of silver nanoparticles in polyelectrolyte multilayer films with controllable internal structures could provide a facile way to ensure the films with enhanced mechanical properties as well as effective anti-bacterial and normal-cell-supporting capabilities.

Sugar-mediated disassembly of mucin/lectin multilayers and their use as pH-Tolerant, on-demand sacrificial layers.

The layer-by-layer (LbL) assembly of thin films on surfaces has proven to be an extremely useful technology for uses ranging from optics to biomedical applications. Releasing these films from the substrate to generate so-called free-standing multilayer films opens a new set of applications. Current approaches to generating such materials are limited because they can be cytotoxic, difficult to scale up, or have undesirable side reactions on the material. In this work, a new sacrificial thin film system capable of chemically triggered dissolution at physiological pH of 7.4 is described. The film was created through LbL assembly of bovine submaxillary mucin (BSM) and the lectin jacalin (JAC) for a (BSM/JAC) multilayer system, which remains stable over a wide pH range (pH 3-9) and at high ionic strength (up to 5 M NaCl). This stability allows for subsequent LbL assembly of additional films in a variety of conditions, which could be released from the substrate by incubation in the presence of a competitive inhibitor sugar, melibiose, which selectively disassembles the (BSM/JAC) section of the film. This novel multilayer system was then applied to generate free-standing, 7 μm diameter, circular ultrathin films, which can be attached to a cell surface as a "backpack". A critical thickness of about 100 nm for the (BSM/JAC) film was required to release the backpacks from the glass substrate, after incubation in melibiose solution at 37 °C for 1 h. Upon their release, backpacks were subsequently attached to murine monocytes without cytotoxicity, thereby demonstrating the compatibility of this mucin-based release system with living cells.

Fabrication of free-standing multilayer films by using pH-responsive microgels as sacrificial layers

A facile way to prepare free-standing polyelectrolyte multilayer films of poly(sodium 4-styrenesulfonate)(PSS)/poly(diallyldimethylammonium)(PDDA) was developed by applying a new pH-dependent sacrificial system based on cross-linked poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) microgels. The tertiary amine groups of PDMAEMA microgels can be protonated in acidic environment, and the protonated microgels were deposited by layer-by-layer (LbL) technique with PSS. PSS/PDDA multilayer films were constructed on the top of the PSS/microgels sacrificial layers. The LbL assembly process was investigated by UV-vis spectroscopy. Further study shows that the free-standing PSS/PDDA multilayer films can be obtained within 3 min by treating the as-prepared films in alkali aqueous solution with a pH of 12.0. The pH-triggered exfoliation of PSS/PDDA multilayer films provides a simple and facile way to prepare LbL assembled free-standing multilayer films.

Free-standing spectral purity filters for extreme ultraviolet lithography

Free-standing multilayer films consisting of Si, Zr, Mo and silicides of both metals have been fabricated and studied as spectral purity filters (SPF) for extreme ultraviolet (EUV) (13.5 nm) lithography tools. Comparative tests of multilayer SPF structures of various compositions have been performed at high power loads. It was found that a Mo/ZrSi2 structure with MoSi2 capping layers is featured with capability to withstand prolonged heating in vacuum (10−7 mbar) at 900-950°C. A technique of fabrication of large aperture free-standing multilayers was developed, and a pilot sample of the above film structure of 160 mm in diameter, 50 nm thick, with transparency at 13.5 nm above 70% was fabricated as a conceptual prototype of SPFs with large dimensions.

Direct Observation of Crack Propagation in Copper–Niobium Multilayers

The failure of a cross-sectional 65 nm-thick copper and 150 nm-thick niobium multilayer thin film was investigated via an in situ transmission electron microscopy straining experiment. The fracture of the free-standing multilayer films was associated with confined dislocation slip within layers containing and preceding the crack tip. Four crack hindrance mechanisms were observed to operate during crack propagation: microvoid formation, crack deviation, layer necking, and crack blunting. Failure was observed to occur across and through the copper and niobium layers but never within the interfaces or grain boundaries. These results are discussed relative to the length-scale-dependent deformation mechanisms of nanoscale metallic multilayers.

Controllable disintegration of temperature-responsive self-assembled multilayer film based on polybetaine

A layer-by-layer (LbL) self-assembly technique was used to construct temperature-responsive multilayer films of polybetaine poly-3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (PDMAPS) and poly(acrylic acid) (PAA). The assembly and disintegration behaviors of PDMAPS/PAA multilayer films were investigated by quartz crystal microbalance (QCM) and atomic force microscopy (AFM). The results indicated that the assembly behaviors of PDMAPS/PAA multilayer films could be well regulated by the pH and temperature of dipping solutions. The disintegration of PDMAPS/PAA multilayer films could be well controlled by varying the disintegration temperature ( T d) and the pH of buffer solution. The critical disintegration temperature ( T cd) decreased with increasing pH of buffer solution used. The ionization of carboxylic acid groups (COOH) of PAA and the breakage of intra-chain associations of PDMAPS in multilayer films are two main reasons for the film disintegration. Based on the controllable disintegration of the PDMAPS/PAA multilayer, free-standing multilayer films were successfully prepared by LbL self-assembly of poly(4-vinylpyridiniomethanecarboxylate) (PVPMC) and PAA using PDMAPS/PAA as a sacrificial sublayer.

Construction and deconstruction of multilayer films containing polycarboxybetaine: Effect of pH and ionic strength

The influences of pH and NaCl concentration of dipping solutions and the pH and NaCl concentration of disintegration solutions on the disintegration behaviors of poly(4-vinylpyridiniomethanecarboxylate) (PVPMC)/poly(sodium 4-styrenesulfonate) (PSS) (PVPMC/PSS) multilayer films were investigated by ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FT-IR), quartz crystal microbalance (QCM) and atomic force microscopy (AFM). It was found that the disintegration rates and degrees of PVPMC/PSS multilayer films in neutral water could be well controlled by changing pH of dipping solutions and immersion time during the disintegration process. Furthermore, PVPMC/PSS multilayer films could be disintegrated completely and rapidly in pH 8 alkali solution or physiological condition (i.e., 0.15 M NaCl solution). The controllable disintegration of PVPMC/PSS multilayer films was then utilized to fabricate PEC/PSS free-standing multilayer films, in which PEC was a positively charged polyelectrolyte complex made from excessive poly(diallyldimethylammonium) (PDDA) and PSS. The experimental results indicated that the disintegration rates of PVPMC/PSS sacrificial sublayer strongly affected the integrity of the resultant PEC/PSS free-standing multilayer films. Only free-floating PEC/PSS was released from neutral water by disintegrating PVPMC/PSS multilayer sublayers. However, large size flat and tube-like PEC/PSS free-standing multilayer films with good mechanical properties were obtained facilely from pH 8 alkali solution and 0.15 M NaCl solution, respectively. The preparation of such free-standing films at physiological condition may be useful in the biological or medical application.

Layer-by-layer self-assembly, controllable disintegration of polycarboxybetaine multilayers and preparation of free-standing films at physiological conditions

The self-assembly and disintegration behavior of polyzwitterion, poly(4-vinylpyridiniomethanecarboxylate) (PVPMC), and negatively charged polyelectrolyte, poly(acrylic acid) (PAA), layer-by-layer (LbL) multilayer films were investigated in detail by using UV-vis absorption spectroscopy, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). The results indicated that the PVPMC/PAA multilayer films grew linearly with increasing bilayer number. The disintegration rate of PVPMC/PAA multilayers could be well controlled by varying the concentration of salt in aqueous solution. It was found that PVPMC/PAA multilayer films could be completely disintegrated in 0.9% normal saline solution within 15 min. Such controllable disintegration behavior rendered the PVPMC/PAA multilayer as an excellent sacrificial sublayer for fabricating free-standing LbL multilayer films. Free-standing multilayer films were then successfully fabricated by LbL self-assembly of positively charged polyelectrolyte complex (PEC), made from poly(diallyldimethylammonium) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS), and negatively charged PSS with PVPMC/PAA as a sacrificial sublayer, which was disintegrated in 0.9% normal saline solution. The obtained free-standing films had good mechanical properties with 24.1 MPa tensile strength at break and 0.56 GPa Young's modulus.

Fabrication of free-standing polyelectrolyte multilayer films: A method using polysulfobetaine-containing films as sacrificial layers

A new pH-dependent sacrificial system based on zwitterionic polysulfobetaine was proposed for the fabrication of free-standing polyelectrolyte multilayer films. The zwitterionic polysulfobetaine, poly(4-vinylpyridine propylsulfobetaine) (P4VPPS), was synthesized and its layer-by-layer (LbL) self-assembly behavior with poly(diallyldimethylammonium) (PDDA) as counterpart was investigated by using UV–vis absorption spectroscopy, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). The LbL multilayer films of PDDA/P4VPPS were successfully constructed in acid aqueous solution at pH 2 with 0.5 M NaCl. The resultant PDDA/P4VPPS multilayer films were pH-dependent and could be disintegrated in alkali aqueous solutions, especially with pH ⩾ 12. This disintegration property rendered such multilayer film as a sacrificial layer for further preparing free-standing polyelectrolyte multilayer films. The PDDA/poly(sodium 4-styrenesulfonate) (PSS) multilayer films deposited on the PDDA/P4VPPS sacrificial layer were confirmed to be successfully released after treated successively by alkali aqueous solution at pH 12 and ethanol. The obtained PDDA/PSS free-standing multilayer films had thicknesses of ca. 847 nm.

Speedy fabrication of free-standing layer-by-layer multilayer films by using polyelectrolyte complex particles as building blocks

A novel method for speedy fabrication of free-standing layer-by-layer (LbL) multilayer films in salt free media, and without the need for a sacrificial sublayer is described by using two different polyelectrolyte complex (PEC) nanoparticles as LbL self-assembly building blocks. Negatively charged polyelectrolyte complex particles (PEC−) consisting of poly(diallyldimethylammonium chloride)/sodium carboxymethyl cellulose (PDDA/CMCNa), and positively charged polyelectrolyte complex particles (PEC+) consisting of PDDA/poly(sodium-p-styrenesulfonate) (PDDA/PSSNa) were prepared and characterized by FT-IR, zeta-potential (ζ potential) and transmission electron microscopy (TEM). The LbL self-assembly of PEC+/PEC− and PDDA/PEC− was followed by quartz crystal microbalance (QCM), optical transmittance, UV-vis absorption spectroscopy and atomic force microscopy (AFM). QCM results show that the thickness growth rate of the PEC+/PEC− pair is 9 times faster than that of the PDDA/PEC− pair and this result is also supported by optical transmittance and UV-vis absorption. A robust free-standing multilayer film of (PEC+/PEC−)25 can be easily peeled off from the substrate after being cross-linked in 3.5 wt% glutaraldehyde (GA) (80 °C, 50mins). Field emission electron scanning microscopy (FESEM) indicates that both the surface and cross-section of the multilayer film display layered structures. Furthermore, multiwall carbon nanotubes (MWCNTs) can also be uniformly incorporated into the free-standing LbL multilayer film by pre-incorporating MWCNTs into PEC− particles. The experimental results show that using oppositely charged PEC particles as LbL assembly components is a speedy and convenient method to fabricate free-standing LbL multilayer films either with or without nanofillers.

Ion-Triggered Exfoliation of Layer-by-Layer Assembled Poly(acrylic acid)/Poly(allylamine hydrochloride) Films from Substrates: A Facile Way To Prepare Free-Standing Multilayer Films

A facile way to prepare sheet- and tubelike free-standing films of poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) was developed by exfoliating PAA/PAH multilayer films from substrates in acid aqueous solution containing copper ions. The exfoliation of the PAA/PAH film from the substrate was achieved by breaking the electrostatic interaction of the PAA layer with the underlying substrate while keeping the integrity of the resultant films. Further study shows that thermally cross-linked free-standing PAA/PAH film can be prepared by treating the film in acid aqueous solution with a pH of 2.0. The ion-triggered exfoliation of PAA/PAH multilayer film provides a simple and flexible way to prepare layer-by-layer (LbL) assembled free-standing multilayer films.