Assembly and mechanical properties of phosphorus dendrimer/polyelectrolyte multilayer microcapsules

We report the preparation, characterization, and mechanical properties of polyelectrolyte/phosphorus dendrimer multilayer microcapsules. The shells of these microcapsules are composed either by alternating poly(styrenesulfonate) (PSS) and positively charged dendrimer G4(NH+Et2Cl-)96 or by alternating poly(allylamine hydrochloride) (PAH) and negatively charged dendrimer G4(CH-COO-Na+)96. The same multilayers were constructed on planar support to examine their layer-by-layer growth and to measure the multilayer thickness. Surface plasmon resonance spectroscopy (SPR) showed regular linear growth of the assembly upon each bilayer deposited. We probe the mechanical properties of these polyelectrolyte/dendrimer microcapsules by measuring force-deformation curves with the atomic force microscope (AFM). The experiment suggests that they are much softer than PSS/PAH microcapsules studied before. This softening is attributed to an enhanced permeability of the polyelectrolyte/dendrimer multilayer shells as compared with multilayers formed by linear polyelectrolytes. In contrast, Young's modulus of both dendrimer-based multilayers was found to be on the same order as that of PSS/PAH multilayers.     

Self-assembly of inner skin hollow fiber polyelectrolyte multilayer membranes by a dynamic negative pressure layer-by-layer technique

In the past studies, electrostatic layer-by-layer (LbL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes (PEMMs). Till now, this method was mainly used to assemble flat sheet and tubular membranes. Since hollow fiber membrane has some advantages such as high-packing density, self-contained mechanical support and hence the consequent economical superiority, this study therefore seeked to assemble inner skin hollow fiber PEMMs by using a dynamic LbL adsorption technique. The assembly process was successfully accomplished by alternatively dynamically filtrating polyacrylic acid (PAA) and polyethyleneimine (PEI) on a hydrolyzed hollow fiber polyacrylonitrile (PAN) membrane under a negative pressure condition. In the case of pervaporation separation of 95 wt.% ethanol–water mixture (50 °C), the membrane obtained with only 4.5 and 6.5 bilayers had separation factor of 245 and 1338 while the permeate fluxes were 290 and 120 g/(m² h), respectively. The pervaporation separation behavior of various alcohol/water mixtures with the alcohols being t-butanol, 2-propanol and ethanol were also investigated. Finally, scanning electron microscopy and atomic force microscopy clearly confirms a uniform and defect-free layer formed on the inner surface of hollow fiber support. Since different polyelectrolyte pairs could be used to assemble PEMMs for different uses, it was expected that the dynamic negative pressure LbL adsorption technique could also potentially be used to prepare many types of PEMMs in other fields.     

Sustained release control via photo-cross-linking of polyelectrolyte layer-by-layer hollow capsules

We describe the formation and permeability of polyelectrolyte multilayer hollow-shell capsules by photo-cross-linking and controlled-release (fluorescence) studies. The hollow shells were prepared by alternate layer-by-layer (LbL) adsorption of photo-cross-linkable benzophenone modified poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) on polystyrene particles, followed by removing the core with tetrahydrofuran. Zeta potential measurements, fourier transform infrared spectroscopy, and transmission electron microscopy were used to verify the LbL process integrity. A model drug, rhodamine B (RB), was successfully loaded into the polyelectrolyte hollow capsules. The release kinetics of RB was investigated using fluorescence spectroscopy. The permeability of RB through the hollow shells was effectively controlled based on UV irradiation time. It was shown that the release of RB molecules can be controlled by the degree of cross-linking induced in the multilayer.     

Salt softening of polyelectrolyte multilayer capsules

The changes in the morphology and the mechanical properties of hollow polyelectrolyte multilayer capsules made from poly(styrenesulfonate)/poly(allylamine hydrochloride) in response to added salt were investigated. We found that capsules shrink in response to salt exposure. The effect depends strongly on the nature of the salt added and follows trends of the Hoffmeister series, with weakly hydrated cations inducing the strongest shrinking. For NaCl, we have investigated additional effects on capsule mechanical properties that are occurring above a 3 M salt concentration and we found that the morphological changes are accompanied by a pronounced softening of the capsule wall material, which we can quantify by analyzing the force response of capsules in the prebuckling regime. This shows that salts can act as plasticizers in the multilayers and induce annealing effects.     

Novel formulations of vitamins and insulin by nanoengineering of polyelectrolyte multilayers around microcrystals

Microcapsules loaded with vitamin K3 (VK3), biotin, or insulin were prepared by using a novel coating technology based on the layer-by-layer (LbL) deposition of oppositely charged polyelectrolytes onto microcrystal templates. This produced multilayered, polymeric shells of varying thickness around the crystalline cores. Dissolution of the core material (VK3 with ethanol, biotin with basic solution, and insulin with acidic solution), resulted in its release through the shells. Microelectrophoresis was employed to monitor the microcrystal coating process; confocal laser scanning microscopy (CLSM) and atomic force microscopy (AFM) were used to verify multilayer coating and the formation of hollow polymer shells following removal of the microcrystal templates. The release rates of both VK3 and insulin decreased as the wall thickness (the number of polyelectrolyte layers deposited onto the microcrystal cores), increased. The release time could be varied by a factor of more than ten, depending on the number of polyelectrolyte layers applied. Following the addition of 70 mass % ethanol, the solubility of VK3 increased by as much as 170-fold, resulting in an increased rate of VK3 release. By selecting appropriate polymer materials for the shells, and by controlling the number of polyelectrolyte layers applied, shells of various thickness, stiffness, aqueous solubility, dispersibility, biocompatibility, and permeability can be constructed.     

Hydrothermal-induced structure transformation of polyelectrolyte multilayers: from nanotubes to capsules

The assembled polyelectrolyte nanotubes composed of poly(styrenesulfonate) and poly(allylamine hydrochloride) multilayers by using the layer-by-layer assembly combined with the porous template method can be transformed into capsules by a high-temperature treatment. Scanning electron microscopy and confocal laser scanning microscopy images revealed the whole transition process. The structure transformation of polyelectrolyte multilayers after annealing can be initiated by the input of thermal energy which leads to a breakage of ion pairs between oppositely charged polyelectrolyte groups. The transition process from tubes to capsules is supposed to be driven by the Raleigh instability and leads to the generated polyelectrolyte capsules with different sizes.     

Photo-cross-linkable polyelectrolyte multilayers for 2-D and 3-D patterning

We report the synthesis of poly(acrylic acid-ran-vinylbenzyl acrylate) (PAArVBA), a photo-cross-linkable weak polyelectrolyte, and its incorporation into polyelectrolyte multilayer (PEM) films. PEM films assembled from PAArVBA and poly(allylamine hydrochloride) (PAH) are found to exhibit similar thickness trends with assembly pH as those previously reported for poly(acrylic acid) (PAA)/PAH multilayers. Swelling properties of the as-built and photo-cross-linked films are studied by in situ ellipsometry. Two-dimensional masking techniques are used to pattern regions of high and low swelling, as confirmed by atomic force microscopy (AFM), and to provide spatial control over the low-pH-induced microporosity transition exhibited by PAH/PAA PEMs. Films containing alternating blocks of PAH/PAArVBA bilayers and PAH/PAA bilayers were assembled, laterally photopatterned, and exposed to low-pH solution to generate nanoporosity leading to patterned Bragg reflectors, thereby demonstrating three-dimensional control over film structure in these weak PEM assemblies.     

Macromolecule encapsulation in diazoresin-based hollow polyelectrolyte microcapsules

A stable enzyme encapsulation technique based on the conversion of weak interactions between diazo resin/poly(styrene sulfonate) to covalent bonds was explored. Photosensitive diazoresin-based polyelectrolyte microcapsules were prepared via layer-by-layer electrostatic self-assembly of poly(styrene sulfonate) and diazoresin on MnCO(3) templates. UV-vis and zeta-potential measurements confirmed the alternate deposition of {PSS/DAR} multilayers on the micrometer-sized dissolvable templates. The DAR-based microcapsules were demonstrated to be permeable to enzymes prior to UV irradiation, while the permeability of the multilayer wall was changed substantially after photo-cross-linking. Encapsulated molecules were stably entrapped after UV irradiation, as shown by confocal microscopy and atomic force microscopy images. Activity assays revealed that encapsulated glucose oxidase possessed 52.8% of the catalytic activity exhibited by the same amount of free enzyme, proving the preservation of native conformation and accessibility of substrate. This encapsulation technique is promising for many biomedical and biotechnological applications, particularly enzyme biosensors, which require stable immobilization of functional components while allowing sufficient transport rates for substrate molecules.     

聚电解质结构及盐浓度对基于DNA和聚阳离子的层层组装型大孔薄膜结构的影响

选择2种不同类型的聚阳离子[强电解质型聚二烯丙基二甲基氯化铵(PDDA)和弱电解质型聚盐酸丙烯胺(PAH)], 分别和脱氧核糖核酸(DNA)分子通过静电吸附作用制备层层组装膜. 利用原子力显微镜和紫外-可见分光光度计研究了聚阳离子结构和组装分子溶液中盐(NaCl)浓度对大孔结构及薄膜生长规律的影响. 结果表明, 在DNA/PDDA体系中, 盐浓度对于大孔结构的形成起到关键性作用. 而对于DNA/PAH薄膜体系, 即使增加DNA或PAH溶液中盐的浓度, 也不会有大孔结构出现, 这主要是由PAH分子的弱电解质特性决定的.     

Thickness and morphology of polyelectrolyte coatings on silica surfaces before and after protein exposure studied by atomic force microscopy

Analyte–wall interaction is a significant problem in capillary electrophoresis (CE) as it may compromise separation efficiencies and migration time repeatability. In CE, self-assembled polyelectrolyte multilayer films of Polybrene (PB) and dextran sulfate (DS) or poly(vinylsulfonic acid) (PVS) have been used to coat the capillary inner wall and thereby prevent analyte adsorption. In this study, atomic force microscopy (AFM) was employed to investigate the layer thickness and surface morphology of monolayer (PB), bilayer, (PB-DS and PB-PVS), and trilayer (PB-DS-PB and PB-PVS-PB) coatings on glass surfaces. AFM nanoshaving experiments providing height distributions demonstrated that the coating procedures led to average layer thicknesses between 1 nm (PB) and 5 nm (PB-DS-PB), suggesting the individual polyelectrolytes adhere flat on the silica surface. Investigation of the surface morphology of the different coatings by AFM revealed that the PB coating does not completely cover the silica surface, whereas full coverage was observed for the trilayer coatings. The DS-containing coatings appeared on average 1 nm thicker than the corresponding PVS-containing coatings, which could be attributed to the molecular structure of the anionic polymers applied. Upon exposure to the basic protein cytochrome c, AFM measurements showed an increase of the layer thickness for bare (3.1 nm) and PB-DS-coated (4.6 nm) silica, indicating substantial protein adsorption. In contrast, a very small or no increase of the layer thickness was observed for the PB and PB-DS-PB coatings, demonstrating their effectiveness against protein adsorption. The AFM results are consistent with earlier obtained CE data obtained for proteins using the same polyelectrolyte coatings.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Mechanical properties of polyelectrolyte-filled multilayer microcapsules studied by atomic force and confocal microscopy

By using a combination of atomic force and confocal microscopy, we explore the deformation properties of multilayer microcapsules filled with a solution of strong polyelectrolyte. Encapsulation of polyelectrolyte was performed by regulation of the multilayer shell permeability in water-acetone solutions. The "filled"capsules prepared by this method were found to be stiffer than "hollow" ones, which reflects the contribution of the excess osmotic pressure to the capsule stiffness. The force-deformation curves contain three distinct regimes of reversible, partially reversible, and irreversible deformations depending on the degree of compression. The analysis of the shape of compressed capsules and of the inner polyelectrolyte spacial distribution allowed one to relate the deformation regimes to the permeability of the multilayer shells for water and inner polyelectrolyte at different stage of compression.     

Mechanical Properties of Poly(dimethylsiloxane)-block-poly(2-methyloxazoline) Polymersomes Probed by Atomic Force Microscopy

Poly(dimethylsiloxane)-block-poly(2-methyloxazoline) (PDMS-b-PMOXA) vesicles were characterized by a combination of dynamic light scattering (DLS), cryogenic transmission electron microscopy (cryo-TEM), and atomic force microscopy imaging and force spectroscopy (AFM). From DLS data, a hydrodynamic radius of ～150 nm was determined, and cryo-TEM micrographs revealed a bilayer thickness of ～16 nm. In AFM experiments on a silicon wafer substrate, adsorption led to a stable spherical caplike conformation of the polymersomes, whereas on mica, adsorption resulted also in vesicle fusion and formation of bilayer patches or multilayer stacks. This indicates a delicate balance between the mechanical stability of PDMS-b-PMOXA polymersomes on one hand and the driving forces for spreading on the other. A Young's modulus of 17 ± 11 MPa and a bending modulus of 7 ± 5 × 10(-18) J were derived from AFM force spectroscopy measurements. Therefore, the elastic response of the PDMS-b-PMOXA polymersomes to external stimuli is much closer to that of lipid vesicles compared to other types of polymersomes, such as polystyrene-block-poly(acrylic acid) (PS-b-PAA).     

Correlating the compliance and permeability of photo-cross-linked polyelectrolyte multilayers

Photo-cross-linkable polyelectrolyte multilayers were made from poly(allylamine) (PAH) and poly(acrylic acid) (PAA) modified with a photosensitive benzophenone. Nanoindentation, using atomic force microscopy (AFM) of these and unmodified PAH/PAA multilayers, was used to assess their mechanical properties in situ under an aqueous buffer. Under the conditions employed (and a 20 nm radius AFM tip), reliable nanoindentations that appeared to be decoupled from the properties of the silicon substrate were obtained for films greater than 150 nm in thickness. A strong difference in the apparent modulus was observed for films terminated with positive as compared to negative polyelectrolytes. Films terminated with PAA were more glassy, suggesting better charge matching of polyelectrolytes. Multilayers irradiated for up to 100 min showed a smooth, controlled increase in the modulus with little change in the water contact angle. The permeability to iodide ion, measured electrochemically, also decreased in a controlled fashion.     

Assembly of poly(N-isopropylacrylamide)-co-acrylic acid microgel thin films on polyelectrolyte multilayers: Effects of polyelectrolyte layer thickness, surface charge, and microgel solution pH

Temperature- and pH-sensitive poly(N-isopropylacrylamide)?Cco-acrylic acid (pNIPAm-co-AAc) microgels were deposited on glass substrates coated with polyelectrolyte multilayers composed of the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(sodium 4-styrenesulfonate) (PSS). The microgel density and structure of the resultant films were investigated as a function of: (1) the number of PAH/PSS layers (layer thickness); (2) the charge on the outer layer of the polyelectrolyte multilayer film; and (3) the pH of microgel deposition solution. The resultant films were studied by differential interference contrast optical microscopy, atomic force microscopy, and scanning electron microscopy. It was found that the coverage of the microgels on the surface was a complex function of the pH of the deposition solution, the charge on the outer layer of the polyelectrolyte thin film and the PAH/PSS layer thickness; although it appears that microgel charge plays the biggest role in determining the resultant surface coverage.     

A new approach for the fabrication of an alternating multilayer film of poly(4-vinylpyridine) and poly(acrylic acid) based on hydrogen bonding

A new approach for the fabrication of a multilayer film assembly is explored, which is based on the alternating assembling of poly(4-vinylpyridine) and poly(acrylic acid) via hydrogen bonding. The homogeneous multilayer films were characterized by UV-Vis, X-ray diffraction and atomic force microscopy (AFM) measurements. The nature of interaction between the two polymers is identified as hydrogen bonding by IR spectroscopy.     

Influence of solvent quality on the growth of polyelectrolyte multilayers

The effect of solvent conditions on the growth of polyelectrolyte (PE) multilayer films comprising poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) on planar substrates was investigated by means of surface plasmon resonance spectroscopy (SPRS), quartz crystal microbalance (QCM), and atomic force microscopy techniques. The solvent quality was varied by the addition of ethanol to the PE solutions used for deposition of the layers, thus tuning the relative strength of electrostatic and secondary intermolecular and intramolecular interactions. Experiments were performed with PE solutions both without added electrolyte and containing 0.5 M NaCl. Decreasing the solvent quality (i.e., increasing the amount of ethanol in the adsorption solution) resulted in a marked increase of both the multilayer film thickness and mass loading, as determined from the SPRS spectra and QCM frequency shifts, respectively. With the solution composition approaching the precipitation point, thick PAH/PSS films were formed due to the screening of the electrostatic intra- and interchain repulsions and enhanced hydrophobic interactions between the polyelectrolyte chains. However, the films formed from water/ethanol mixtures remained stable upon subsequent exposure to water or salt-containing solutions: no significant film desorption occurred after up to 24 h of exposure to water or 0.5 M NaCl solutions. In addition, the effect of postdeposition exposure to water/ethanol mixtures was investigated for PE multilayers assembled from aqueous solutions. In this case, the optical thickness of the films was determined during exposure to water/ethanol mixtures, and instead of swelling, the polyelectrolyte films collapse to the surface as a result of the unfavorable segment-solvent interactions.     

Nanostructured micellar films formed via layer-by-layer deposition of photoactive polymer

Photoactive nanostructured micellar films were prepared from the amphiphilic copolymer poly(sodium styrenesulfonate- stat-2-vinylnaphthalene) (PSSS- stat-VN) and cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) or poly(allylamine hydrochloride) (PAH) on quartz and silicon substrates via layer-by-layer (LbL) electrostatic self-assembly. The macromolecules of this amphiphilic copolymer adopt a coiled micellar conformation in aqueous solution that is preserved in the films as evidenced by atomic force microscopy (AFM) and spectroscopic studies. The hydrophobic domains present in the film can serve as host sites for various organic molecules. The probe molecules reside in those isolated nanosize domains. Their aggregation and quenching of their emission is eliminated. The experiments showed a regular growth of multilayer thickness and the content of solubilized compounds in the films. Thus, a defined amount of the hydrophobic compounds of interest may be introduced into these water-processable polymeric films. Some stratification of the films was induced by the presence of stiff nanoparticle-like micelles. That makes these films an important new material for studies of photoinduced energy and electron transfer.     

Thermal behavior of polyelectrolyte multilayer microcapsules. 1. The effect of odd and even layer number

The temperature-dependent behavior of hollow polyelectrolyte multilayer capsules consisting of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sulfonate) (PSS) with a different number of layers was investigated in aqueous media using confocal laser scanning microscopy, scanning and transmission electron microscopy, atomic force microscopy, and elemental analysis. Capsules with an even number of layers exhibited a pronounced shrinking at elevated temperature resulting in a transition to a dense sphere, whereas capsules with an odd number of layers swelled during heating to 5-fold of their initial size followed by their rupture. This effect increases for odd layer numbers and decreases for even layer numbers with increasing layer number. According to elemental analysis, an excess of PDADMAC monomers exists within the multilayers of capsules with an odd number of layers leading to a repulsion between the positive charges, whereas shells with an even number of layers have a balanced ratio between the oppositely charged polyions, so that the temperature-dependent behavior is controlled by the different interactions between polyelectrolytes and the bulk water. At a certain temperature, the polyelectrolyte material softens thus facilitating any rearrangement. Besides incubation temperature, the duration of heating has an influence on the restructuring of the multilayers.     

Small angle neutron scattering investigations (SANS) of polyelectrolyte multilayer capsules templated on human red blood cells

Polyelectrolyte capsules were fabricated by layer-by-layer deposition of poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) on glutardialdehyde fixed human erythrocytes and subsequent core dissolution using NaOCl as an oxidizing agent. SANS together with confocal laser scanning microscopy (CLSM) were applied to study capsule topology and interior as well as the layer thickness as a function of the deposition protocol, layer number, ionic concentration, and temperature treatment. The capsules contained various amounts of trapped polyelectrolyte. Retention depended on the order of polyelectrolyte deposition and layer number, which influenced layer permeability. The capsule wall thickness was found to be much smaller (3-4.5 nm in total) than what was known for polyelectrolyte multilayer walls, where every single layer contributes about 1.8 nm to the total thickness. NaCl (0.1 mM) caused a layer thickness decrease by 16%. Annealing at 70 degrees C induced capsule shrinking together with an increase of the wall thickness by 85% and wall density by 12%.