Stimuli-responsive polyelectrolyte multilayer films and microcapsules.

Polyelectrolyte multilayer (PEM) films and particularly hollow capsules composed of PEM shells have gained significant interest since their introduction. Their compositional versatility and easiness of preparation via so-called layer-by-layer assembly led to the development of numerous systems containing also stimuli-responsive components. This paper reviews the achievements related to the formation, determination of structure, and properties of PEM films and capsules responding to major physical, chemical, and biological stimuli. Their applications as e.g., microcarriers for controlled delivery release of active components, substrates for controlled cells' growth, coatings for enhanced surface adhesion, or self-healing anticorrosive systems are shown and discussed. The influence of various stimuli on integrity, permeability of the films or capsules shell are presented together with related applications in biomedicine for controlled drug release as well as in biotechnology and industrial protective coatings.

Structural evolution of supported lipid bilayers intercalated with quantum dots.

HYPOTHESIS: Supported lipid bilayers (SLBs) embedded with hydrophobic quantum dots (QDs) undergo temporal structural rearrangement. EXPERIMENTS: Synchrotron X-ray reflectivity (XRR) was applied to monitor the temporal structural changes over a period of 24 h of mixed SLBs of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) / 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-ethanolamine (POPE) intercalated with 4.9 nm hydrophobic cadmium sulphide quantum dots (CdS QDs). The QD-embedded SLBs (QD-SLBs) were formed via rupture of the mixed liposomes on a positively charged polyethylene imine (PEI) monolayer. Atomic force microscopy (AFM) imaging provided complementary characterization of the bilayer morphology. FINDINGS: Our results show time-dependent perturbations in the SLB structure due to the interaction upon QD incorporation. Compared to the SLB without QDs, at 3 h incubation time, there was a measurable decrease in the bilayer thickness and a concurrent increase in the scattering length density (SLD) of the QD-SLB. The QD-SLB then became progressively thicker with increasing incubation time, which - along with the fitted SLD profile - was attributed to the structural rearrangement due to the QDs being expelled from the inner leaflet to the outer leaflet of the bilayer. Our results give unprecedented mechanistic insights into the structural evolution of QD-SLBs on a polymer cushion, important to their potential biomedical and biosensing applications.

Supported lipid bilayers with encapsulated quantum dots (QDs) via liposome fusion: effect of QD size on bilayer formation and structure.

Understanding interactions between functional nanoparticles and lipid bilayers is important to many emerging biomedical and bioanalytical applications. In this paper, we report incorporation of hydrophobic cadmium sulphide quantum dots (CdS QDs) into mixed 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) liposomes, and into their supported bilayers (SLBs). The QDs were found embedded in the hydrophobic regions of the liposomes and the supported bilayers, which retained the QD fluorescent properties. In particular, we studied the effect of the QD size (2.7-5.4 nm in diameter) on the formation kinetics and structure of the supported POPC/POPE bilayers, monitored in situ using quartz crystal microbalance with dissipation monitoring (QCM-D), as the liposomes ruptured onto the substrate. The morphology of the obtained QD-lipid hybrid bilayers was studied using atomic force microscopy (AFM), and their structure by synchrotron X-ray reflectivity (XRR). It was shown that the incorporation of hydrophobic QDs promoted bilayer formation on the PEI cushion, evident from the rupture and fusion of the QD-endowed liposomes at a lower surface coverage compared to the liposomes without QDs. Furthermore, the degree of disruption in the supported bilayer structure caused by the QDs was found to be correlated with the QD size. Our results provide mechanistic insights into the kinetics of the rupturing and formation process of QD-endowed supported lipid bilayers via liposome fusion on polymer cushions.

Properties of POPC/POPE supported lipid bilayers modified with hydrophobic quantum dots on polyelectrolyte cushions.

The formation and properties of supported lipid bilayers (SLB) containing hydrophobic nanoparticles (NP) was studied in relation to underlying cushion obtained from selected polyelectrolyte multilayers. Lipid vesicles were formed from zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and negatively charged 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) in phosphate buffer (PBS). As hydrophobic nanoparticles - quantum dots (QD) with size of 3.8nm (emission wavelength of 420nm) were used. Polyelectrolyte multilayers (PEM) were constructed by the sequential, i.e., layer-by-layer (LbL) adsorption of alternately charged polyelectrolytes from their solutions. Liposomes and Liposome-QDs complexes were studied with Transmission Cryo-Electron Microscopy (Cryo-TEM) to verify the quality of vesicles and the position of QD within lipid bilayer. Deposition of liposomes and liposomes with quantum dots on polyelectrolyte films was studied in situ using quartz crystal microbalance with dissipation (QCM-D) technique. The fluorescence emission spectra were analyzed for both: suspension of liposomes with nanoparticles and for supported lipid bilayers containing QD on PEM. It was demonstrated that quantum dots are located in the hydrophobic part of lipid bilayer. Moreover, we proved that such QD-modified liposomes formed supported lipid bilayers and their final structure depended on the type of underlying cushion.

Effect of Supporting Polyelectrolyte Multilayers and Deposition Conditions on the Formation of 1-Palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine/1-Palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine Lipid Bilayers.

The formation of complete supported lipid bilayers by vesicle adsorption and rupture was studied in relation to deposition conditions of vesicles and underlying cushion formed from various polyelectrolytes. Lipid vesicles were formed from zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and negatively charged 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) in phosphate buffer of various pH with or without NaCl addition. Polyelectrolyte multilayer films (PEM) were constructed by sequential adsorption of alternately charged polyelectrolytes from their solutions-layer-by-layer deposition (LBL). The mechanism of the formation of supported lipid bilayer on polyelectrolyte films was studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). QCM-D allowed following the adsorption kinetics while AFM measurements verified the morphology of lipid vesicles and isolated bilayer patches on the PEM cushions providing local topological images in terms of lateral organization. Additionally, polyelectrolyte cushions were characterized with ellipsometry to find thickness and swelling properties, and their roughness was determined using AFM. It has been demonstrated that the pH value and an addition of NaCl in the buffer solution as well as the type of the polyelectrolyte cushion influence the kinetics of bilayer formation and the quality of formed bilayer patches.