Layer-by-layer multilayered film has been creating great opportunities in developing controlled drug and other bioactive molecular delivery system. In this work, coumarin bearing micelles of poly(acrylic acid-coumarin methacrylate) is first synthesized in a one-step copolymerization and the reversible photo-crosslinkable multilayers containing coumarin groups are then fabricated via layering the micelles with polyethyleneimine (PEI). The film growth behavior of polyetheleneimine/poly(acrylic acid-coumarin methacrylate) (PEI/P(AA-r-CMA)) multilayer is found to rely on deposit solution pH. Increasing PEI solution pH and decreasing P(AA-r-CMA) pH can greatly accelerate film growing process. This is explained by PEI diffusivity and destabilization of P(AA-r-CMA) micelle at solution/multilayer interface. Nile red (NR) is loaded into the film as a model drug via simple post diffusion driven by hydrophobic interactions. Furthermore, photo-crosslink and decrosslink of PEI/P(AA-r-CMA) film is achieved by irradiating the films with light of 365 and 254 nm wavelength, respectively, which therefore ensures the possibility of fine control over drug delivery procedure. 相似文献
The buildup of poly(L-glutamic acid) (PGA) and poly(L-lysine) (PLL) multilayers on silica and titanium surfaces, with and without an initial layer of polyethyleneimine (PEI), was investigated and characterized by means of in situ ellipsometry and quartz crystal microbalance with dissipation. A two-regime buildup was found in all systems, where the length of the first slow-growing regime is dependent on the structure of the initial layers. In the second fast-growing regime, the film thickness grows linearly while the mass increases more than linearly (close to exponentially) with the number of deposited layers. The film refractive indices as well as the water contents indicate that the film density changes as the multilayer film builds up. The change in film density was proposed to be due to polypeptides diffusing into the multilayer film as they attach. Furthermore, the use of PEI as the initial layer was found to induce a difference in the thickness increments for PGA and PLL. 相似文献
Here we report fabrication of artificial free-standing yeast biofilms built using sacrificial calcium carbonate-coated templates and layer-by-layer assembly of extracellular matrix-mimicking polyelectrolyte multilayers. The free-standing biofilms are freely floating multilayered films of oppositely charged polyelectrolytes and live cells incorporated in the polyelectrolyte layers. Such biofilms were initially formed on glass substrates of circular and ribbon-like shapes coated with thin layers of calcium carbonate microparticles. The templates were then coated with cationic and anionic polyelectrolytes to produce a supporting multilayered thin film. Then the yeast alone or mixed with various micro- and nanoparticle inclusions was deposited onto the multilayer composite films and further coated with outer polyelectrolyte multilayers. To detach the biofilms from the glass substrates the calcium carbonate layer was chemically dissolved yielding free-standing composite biofilms. These artificial biofilms to a certain degree mimic the primitive multicellular and colonial species. We have demonstrated the added functionality of the free-standing artificial biofilms containing magnetic, latex and silver micro- and nanoparticles. We have also developed "symbiotic" multicellular biofilms containing yeast and bacteria. This approach for fabrication of free-standing artificial biofilms can be potentially helpful in development of artificial colonial microorganisms composed of several different unicellular species and an important tool for growing cell cultures free of supporting substrates. 相似文献
The influence of a first (anchoring) layer and film treatment on the structure and properties of polyelectrolyte multilayer (PEM) films obtained from polyallylamine hydrochloride (PAH) and polysodium 4-styrenesulfonate (PSS) was studied. Branched polyethyleneimine (PEI) was used as an anchoring layer. The film thickness was measured by ellipsometry. Complementary X-ray reflectometry and AFM experiments were performed to study the change in the interfacial roughness. We found that the thickness of the PEM films increased linearly with the number of layers and depended on the presence of an anchoring PEI layer. Thicker films were obtained for multilayers having PEI as the first layer comparing to films having the same number of layers but consisting of PAH/PSS only. We investigated the wettability of PEM surfaces using direct image analysis of the shape of sessile water drops. Periodic oscillations in contact angle were observed. PAH-terminated films were more hydrophobic than films with PSS as the outermost layer. The effect of long time conditioning of PEM films in solutions of various pH's or salt (NaCl) concentrations was also examined. Salt or base solutions induced modification in wetting properties of the polyelectrolyte multilayers but had a negligible effect on the film thickness. 相似文献
We present a new way to protect polyelectrolyte multilayers from water, consisting in the adsorption and subsequent fusing of charged wax particles atop a multilayer. The formation of the wax layer is demonstrated by different techniques such as ellipsometry, contact angle measurements, and atomic force microscopy. The diffusion of water in protected and unprotected multilayers is studied by in situ neutron reflectometry. Whereas a top layer of wax crystals already allows substantial reduction of the diffusion, the fusion of this top layer leads to the dominating exclusion of water from the multilayers when dipped in water. This method opens up new interesting avenues for polyelectrolyte multilayers in practical applications where permeability of water, ions, or hydrophilic drugs is an issue. 相似文献
The growth of polysaccharide multilayers consisting of positively charged chitosan (CH) and negatively charged heparin (HEP) was monitored in situ by employing a quartz crystal microbalance (QCM-D) and dual-polarization interferometry (DPI). The main focus was on how the physicochemical properties of the solution affect the growth and structure of the resulting multilayer film. These results showed that when increasing the ionic strength of the polysaccharide solutions at a fixed pH, both the "dry" (optical) (DPI) mass and wet (QCM) mass of the adsorbed multilayer film increased. The same effect was found when increasing the pH while keeping the ionic strength constant. Furthermore, the growth of multilayers showed an exponential-like behavior independent of the solution conditions that were used in this study. It was also established that chitosan was the predominant species present in the chitosan-heparin multilayer film. We discuss the viscoelastic properties of the adsorbed layers and their variation during the multilayer buildup. Interestingly and contrary to common interpretation of the QCM-D results, we found that under one particular solution condition (pH 4.2 and 30 mM NaCl) the increase in the dissipation of oscillation energy from the adsorbed layer was a consequence of layer stiffening rather than indicating a more hydrated and viscous film. On the basis of the widely used Voigt viscoelastic model for an adsorbed layer, we show that it is the film viscosity and shear that define the layer viscoelasticity (structure) of the film and not the absolute value of energy dissipation, which in fact can be very misleading. 相似文献
Summary: The multilayers of polycation‐based non‐viral DNA nanoparticles and biodegradable poly(L ‐glutamic acid) (PGA) were constructed by a layer‐by‐layer (LbL) technique. Poly(ethyleneimine) (PEI) was used to condense DNA to develop non‐viral DNA nanoparticles. AFM, UV‐visible spectrometry, and TEM measurements revealed that the PEI‐DNA nanoparticles were successfully incorporated into the multilayers. The well‐structured, easily processed multilayers with the non‐viral DNA nanoparticles may provide a novel approach to precisely control the delivery of DNA, which may have great potential for gene therapy applications in tissue engineering, medical implants, etc.
A TEM image of the cross section of a (PGA/PEI‐DNA nanoparticle)20 multilayer. 相似文献
Application of polyelectrolyte multilayer (PEM) capsules as vehicles for the controlled delivery of substances, such as drugs, genes, pesticides, cosmetics, and foodstuffs, requires a sound understanding of the permeability of the capsules. We report the results of a detailed investigation into probing capsule permeability via a molecular beacon (MB) approach. This method involves preparing MB-functionalized bimodal mesoporous silica (BMSMB) particles, encapsulating the BMSMB particles within the PEM film to be probed, and then incubating the encapsulated BMSMB particles with DNA target sequences of different lengths. Permeation of the DNA targets through the capsule shell causes the immobilized MBs to open due to hybridization of the DNA targets with the complementary loop region of the MBs, resulting in an increase in the MB fluorescence. The assay conditions (BMSMB particle concentration, MB loading within the BMS particles, DNA target concentration, DNA target size, pH, sodium chloride concentration) where the MB-DNA sensing process is effective were first examined. The permeability of DNA through poly(sodium 4-styrenesulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) multilayer films, with and without a poly(ethyleneimine) (PEI) precursor layer, was then investigated. The permeation of the DNA targets decreases considerably as the thickness of the PEM film encapsulating the BMSMB particles increases. Furthermore, the presence of a PEI precursor layer gives rise to less permeable PSS/PAH multilayers. The diffusion coefficients calculated for the DNA targets through the PEM capsules range from 10-19 to 10-18 m2 s-1. This investigation demonstrates that the MB approach to measuring permeability is an important new tool for the characterization of PEM capsules and is expected to be applicable for probing the permeability of other systems, such as membranes, liposomes, and emulsions. 相似文献
We show, in this paper that multivalent ferrocyanide anions can penetrate into exponentially growing (PGA/PAH)n multilayer films whatever the nature of the last deposited layer. These ions are not able to diffuse out of the film when it is brought in contact with a pure buffer solution. However, the contact of this film with a poly(allylamine) (PAH) or a poly(L-glutamic acid) (PGA) solution leads to the release of ferrocyanide ions from the multilayer. It is shown that the release of ferrocyanide anions, when the film is in contact with a PGA solution, is due to the diffusion of the PGA chains into the film so that an exchange between ferrocyanide ions and PGA chains takes place inside the film. On the other hand, PAH chains do not diffuse into PGA/PAH multilayers. When the film is then brought in contact with a PAH solution, the PAH chains from the solution are expected to strongly interact with the ferrocyanide ions and thus induce a diffusion mechanism of the multivalent anions out of the film, the film/solution interface playing the role of a sink for these ions. This work thus shows that interactions between multivalent ions and exponentially growing films are much more complex than expected at first sight and that polyelectrolyte multilayers must be seen as dynamic entities in which diffusion and exchange processes can take place. 相似文献
