Peculiarities of polyelectrolyte multilayer assembly on patterned surfaces

The layer-by-layer assembly of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate) is studied on templates with imprinted arrays of microwells ranging from 2 to 25 μm and different aspect ratios. The thickness and microstructure of polyelectrolyte multilayers (PEMs) are measured using scanning electron microscopy. At 0.2 M ionic strength, the PEM film evenly coats the template both inside and outside the microwells. If the film is thinner than the critical value of about 400 nm, PEM microstructures collapse upon dissolving the template. Euler's model of critical stress is used to describe the collapse. At 2 M ionic strength, a substantially thinner PEM film is assembled inside the 25 μm wells than outside. If the well diameter is reduced to 7 and 2 μm, a much thicker PEM film is formed inside the microwells. These observations have been attributed to the changing of polyelectrolyte conformation in the solutions.     

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.     

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.     

Individually Addressable Patterned Multilayer Microchambers for Site‐Specific Release‐On‐Demand

Patterned arrays of light‐responsive microchambers are suggested as candidates for site‐specific release of chemicals in small and precisely defined quantities on demand. A composite film is made of poly(allylammonium)‐poly(styrene sulfonate) multilayers and gold nanoparticles incorporated between subsequent stacks of polyelectrolytes. The film shaped as microchambers is loaded with colloid particles or oil‐soluble molecules. The microchambers are sealed onto a glass slide precoated with an adhesive poly(diallyldimethylammonium)‐poly(styrene sulfonate) multilayer film. A focused laser beam is used for remote addressing the individual microchambers and site‐specific release of the loaded cargo.     

Probing the permeability of polyelectrolyte multilayer capsules via a molecular beacon approach

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.     

Kinetic stability of water-dispersed oil droplets encapsulated in a polyelectrolyte multilayer shell

The original theoretical model of polyelectrolyte adsorption onto water-dispersed colloid particles is extended to the system of polydisperse droplets of sunflower oil. Polycation (poly(allylamine hydrochloride)) and polyanion (poly(sodium 4-styrenesulfonate)) are taken in the theoretically projected concentrations to perform Layer-by-Layer assembly of a multilayer shell on the surface of oil droplets preliminary stabilized with a protein emulsifier (bovine serum albumin). The velocity of gravitational separation in suspension of encapsulated oil droplets is theoretically predicted and experimentally measured depending on the coating shell's thickness, aiming to clarify the mechanism to control over the separation process. Combining the theory and experimental data, the mass density of a polyelectrolyte multilayer shell assembled in a Layer-by-Layer fashion is obtained. Polyelectrolyte multilayer coated oil droplets are characterized by means of ζ-potential, and particle size measurements, and visualized by scanning electron microscopy.     

Bioassisted synthesis of catalytic gold/silica nanotubes using layer-by-layer assembled polypeptide templates

We report the bioassisted synthesis of gold nanoparticle/silica (Au NP/silica) tubes using layer-by-layer (LBL) assembled poly(L-lysine)/poly(L-tyrosine) (PLL/PLT) multilayer films deposited on the polycarbonate (PC) membrane pores as both mediating agents and templates. The novelty of this approach is the in situ synthesis of Au NP/silica tubes using PLL/PLT multilayer films for sequential growth of Au NPs and silicas. The experimental data revealed that the buildup of the LBL multilayer films was mainly driven by the formation of hydrogen bond and the polypeptide macromolecular assemblies adopted mainly β-sheet conformation. The as-prepared Au NP/silica tubes possessed promising catalytic activity toward the reduction of p-nitrophenol. The synthesis conditions such as the concentration of gold precursor and polypeptide molecular weight were found to influence the gold weight ratio and particle size in the tubes and the catalytic properties of the Au NP/silica tubes. This approach provides a facile, robust, and green method to obtain nonaggregated metal nanoparticles immobilized in porous oxide network at ambient conditions. Using the synergy between biomimetic or bioassisted synthesis of nanostructured materials and LbL assembly technique, a variety of structures such as films, tubes, and capsules comprising of multiple compositions can be obtained.     

Modulation of hemocompatibility of polysulfone by polyelectrolyte multilayer films

Polyelectrolyte multilayer (PEM) films have been recently applied to surface modification of biomaterials. Cellular interactions with PEM films consisted of weak polyelectrolytes are greatly affected by the conditions of polyelectrolyte deposition, such as pH of polyelectrolyte solution. Previous studies indicated that the adhesion of several types of mammalian cells to PAH/PAA multilayer films was hindered by low pH and high layer numbers. The objective of this study is to evaluate whether the hemocompatibility of polysulfone can be modulated by deposition of poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) multilayer films. PAH/PAA multilayer films with different layer numbers were assembled onto polysulfone at either pH 2.0 or pH 6.5. The number of platelet adhesion and the morphology of adherent platelets were determined to evaluate hemocompatibility of modified substrates. Compared to non-treat polysulfone, the PEM films developed at pH 2.0 decreased platelet adhesion, while those built at pH 6.5 enhanced platelet deposition. Platelet adhesion was found positively correlated to polyclonal antibodies binding to surface-bound fibrinogen. The extent of platelet spreading was increased with layer numbers of PEM films, suggesting that the adherent platelets on thick PEM films were prone to activation. In conclusion, PAH/PAA films with few layers developed at pH 2.0 possessed better hemocompatibility compared to other substrates.     

Fibronectin adsorption onto polyelectrolyte multilayer films

The Layer-by-layer deposition of positively and negatively charged macromolecular species is an ideal method for constructing thin films incorporating biological molecules. We investigate the adsorption of fibronectin onto polyelectrolyte multilayer (PEM) films using optical waveguide lightmode spectroscopy (OWLS) and atomic force microscopy (AFM). PEM films are formed by adsorption onto Si(Ti)O2 from alternately introduced flowing solutions of anionic poly(sodium 4-styrenesulfonate) (PSS) and cationic poly(allylamine hydrochloride) (PAH). Using OWLS, we find the initial rate and overall extent offibronectin adsorption to be greatest on PEM films terminated with a PAH layer. The polarizability density of the adsorbed protein layer, as measured by its refractive index, is virtually identical on both PAH- and PSS-terminated films; the higher adsorbed density on the PAH-terminated film is due to an adsorbed layer of roughly twice the thickness. The binding of monoclonal antibodies specific to the protein's cell binding site is considerably enhanced to fibronectin adsorbed to the PSS layer, indicating a more accessible adsorbed layer. With increased salt concentration, we find thicker PEM films but considerably thinner adsorbed fibronectin layers, owing to increased electrostatic screening. Using AFM, we find adsorbed fibronectin layers to contain clusters; these are more numerous and symmetric on the PSS-terminated film. By considering the electrostatic binding of a segmental model fibronectin molecule, we propose a picture of fibronectin adsorbed primarily in an end-on-oriented monolayer on a PAH-terminated film and as clusters plus side-on-oriented isolated molecules onto a PSS-terminated film.     

“Noodle-like” Mesoporous Silica Templated by Polyelectrolyte／Surfactant Complex

“Noodle-like” mesoporous silica with a diameter of about 180 nm and a length of ca. 10μm was prepared through sol-gel process by using poly(sodium 4-styrenesulfonate) (PSS)/cetyltrimethylammonium bromide (CTAB) complex as template. Parallel oriented regular mesopores with a diameter of around 2-4 nm are distributed along the wall of the particles, while the “worm-like” disordered mesopores can be found in the fringe part. This approach provides a new series of templates and a novel route to prepare inorganic mesoporous materials with special morphology.     

PET/PC共混体系的酯交换反应对其高压结晶行为的影响

利用转矩流变仪、DSC、SEM及WAXD等表征手段研究了PET/PC共混体系的酯交换反应对其高压结晶行为的影响.SEM观察表明,PET和PC熔混时的酯交换反应有利于PET/PC体系在高压结晶时生成厚度较大的伸直链晶体,且可以促进其高压下酯交换反应的发生.楔形伸直链晶体和弯曲伸直链晶体的存在证明链滑移扩散和酯交换反应两种机制对体系中聚酯伸直链晶体的增厚有贡献.拟合分峰法和War-ren-Averbach傅里叶分析法的计算结果表明,随PET/PC体系熔混时酯交换反应程度的增加,高压结晶共混物的结晶度降低,PET的平均微晶尺寸增大,点阵畸变平均值则减小,而微晶尺寸分布变宽.提出了在共聚物组分都具备结晶能力时,结晶诱导化学反应和化学反应诱导结晶两种过程在一定条件下可同时发生的观点.     

胶体颗粒在聚电解质多层膜表面的可控组装

利用原子力显微镜和扫描电子显微镜研究了磺化聚苯乙烯胶体颗粒在由聚二甲基二烯丙基氯化铵和聚苯乙烯磺酸钠层状自组装而成的多层膜表面的组装.该组装受表面性质影响,通过对多层膜的最外层的组装条件或利用盐溶液对多层膜进行后处理可以控制胶体颗粒在膜表面的组装密度.     

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.     

Photopatterned nanoporosity in polyelectrolyte multilayer films

We report on spatial control of nanoporosity in polyelectrolyte multilayer (PEM) films using photopatterning and its effects on film optical and adsorption properties. Multilayers assembled from poly(acrylic acid-ran-vinylbenzyl acrylate) (PAArVBA), a photo-cross-linking polymer, and poly(allylamine hydrochloric acid) (PAH) were patterned using ultraviolet light followed by immersion in low pH and then neutral pH solutions to induce nanoporosity in unexposed regions. Model charged small molecules rhodamine B, fluorescein, and propidium iodide and the model protein albumin exhibit increased adsorption to nanoporous regions of patterned PEM films as shown by fluorescence microscopy and radiolabeling experiments. Films assembled with alternating stacks of PAH/poly(sodium-4-styrene sulfonate) (SPS), which do not become nanoporous, and stacks of PAH/PAArVBA were patterned to create nanoporous capillary channels. Interdigitated channels demonstrated simultaneous, separate wicking of dimethyl sulfoxide-solvated fluorescein and rhodamine B. In addition, these heterostack structures exhibited patternable Bragg reflectivity of greater than 25% due to refractive index differences between the nanoporous and nonporous stacks. Finally, the PEM assembly process coupled with photo-cross-linking was used to create films with two separate stacked reflective patterns with a doubling in reflectivity where patterns overlapped. The combined adsorptive and reflective properties of these films hold promise for applications in diagnostic arrays and therapeutics delivery.     

Stable aqueous nanoparticle film assemblies with covalent and charged polymer linking networks

The construction of highly stable and efficiently assembled multilayer films of purely water soluble gold nanoparticles is reported. Citrate-stabilized nanoparticles (CS-NPs) of average core diameter of 10 nm are used as templates for stabilization-based exchange reactions with thioctic acid to form more robust aqueous NPs that can be assembled into multilayer films. The thioctic acid stabilized nanoparticles (TAS-NPs) are networked via covalent and electrostatic linking systems, employing dithiols and the cationic polymer poly(L-lysine), respectively. Multilayer films of up to 150 nm in thickness are successfully grown at biological pH with no observable degradation of the NPs within the film. The characteristic surface plasmon band, an optical feature of certain NP film assemblies that can be used to report the local environment and core spacing within the film, is preserved. Growth dynamics and film stability in solution and in the air are examined, with poly(L-lysine) linked films showing no evidence of aggregation for at least 50 days. We believe these films represent a pivotal step toward exploring the potential of aqueous NP film assemblies as a sensing apparatus.     

New 2-in-1 polyelectrolyte step-by-step film buildup without solution alternation: from PEDOT-PSS to polyelectrolyte complexes

Although never emphasized and increasingly used in organic electronics, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) layer-by-layer (lbl) film construction violates the alternation of polyanion and polycation rule stated as a prerequisit for a step-by-step film buildup. To demonstrate that this alternation is not always necessary, we studied the step-by-step construction of films using a single solution containing polycation/polyanion complexes. We investigated four different systems: PEDOT-PSS, bPEI-PSS (branched poly(ethylene imine)-poly(sodium 4-styrene sulfonate)), PDADMA-PSS (poly(diallyl dimethyl ammonium)-PSS), and PAH-PSS (poly(allylamine hydrochloride)-PSS). The film buildup obtained by spin-coating or dipping-and-drying process was monitored by ellipsometry, UV-vis-NIR spectrophotometry, and quartz-crystal microbalance. The surface morphology of the films was characterized by atomic force microscopy in tapping mode. After an initial transient regime, the different films have a linear buildup with the number of deposition steps. It appears that, when the particles composed of polyanion-polycation complex and complex aggregates in solution are more or less liquid (case of PEDOT-PSS and bPEI-PSS), our method leads to smooth films (roughness on the order of 1-2 nm). On the other hand, when these complexes are more or less solid particles (case of PDADMA-PSS and PAH-PSS), the resulting films are much rougher (typically 10 nm). Polycation/polyanion molar ratios in monomer unit of the liquid, rinsing, and drying steps are key parameters governing the film buildup process with an optimal polycation/polyanion molar ratio leading to the fastest film growth. This new and general lbl method, designated as 2-in-1 method, allows obtaining regular and controlled film buildup with a single liquid containing polyelectrolyte complexes and opens a new route for surface functionalization with polyelectrolytes.     

Modulation of the functions of osteoblast-like cells on poly(allylamine hydrochloride) and poly(acrylic acid) multilayer films

Deposition of layer-by-layer polyelectrolyte multilayer (PEM) films has been a widely applied surface modification technique to improve the biocompatibility of biomaterials. The objective of this study was to investigate the impact of the deposition of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) multilayer films on adhesion, growth and differentiation of osteoblasts-like MG63 cells. PAH and PAA were deposited sequentially onto tissue culture polystyrene at either pH 2.0 or pH 6.5 with 4-21 layers. While the MG63 cells attached poorly on the PAH/PAA multilayer films deposited at pH 2.0, while the cells adhered to the PEM films deposited at pH 6.5, depending on layer numbers. Cell adhesion, proliferation and osteogenic activities (alkaline phosphatase activity, expression of osteogenic marker genes and mineralization) were highest on the 4-layer PAH/PAA film and decreased with increasing layer numbers. On the other hand, the behavior of MG63 cells did not show any difference on the adjacent even and odd layers, except PEM4 and PEM5, i.e. the surface charges of the PAH/PAA multilayer films with over ten layers seem indifferent to osteoblastic functions. The results in this study suggested that the mechanical properties of PEM films may play a critical role in modulating the behavior of osteoblasts, providing guidance for application of PEM films to osteopaedic implants.     

A mechanically strong conductive hydrogel reinforced by diaminotriazine hydrogen bonding

Over the past decades,the urgent need for high strength conductive hydrogels in diverse applications has motivated an unremitting effort to combine the improved mechanical properties of hydrogels with conductive performances.In this work,high strength conductive hydrogels intensified with intermolecular hydrogen bonding are fabricated by in situ mixing poly(2-vinyl-4,6-diamino-1,3,5-triazine-co-polyethylene glycol diacrylates) (PVDT-PEGDA) hydrogels with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT/PSS).The conductive hydrogels in deionized water exhibit high mechanical performances with compressive strength and tensile strength in the range of 7.58-9.52 MPa and 0.48-1.20 MPa respectively,which are ascribed to the intermolecular hydrogen bonding interactions of diaminotriazinediaminotriazine (DAT-DAT) in the network.Meanwhile,adding PEDOT/PSS can significantly increase both the specific conductivities and equilibrium water contents of the hydrogels.These cytocompatible conductive hydrogels may have a great potential to be used as electrical stimuli responsive soft biomaterials.     

Nonlithographic micro- and nanopatterning of TiO2 using polymer stamped molecular templates

The polymer-on-polymer stamping technique was used to template patterned TiO2 onto polymer thin films. Polystyrene-b-polyvinyl pyridine diblock copolymer (PS-b-PVP) was stamped on a layer-by-layer assembled thin film of poly(allylamine hydrochloride) and poly(acrylic acid). After rinsing the surface with a good solvent for the block copolymer, an adsorbed PS-b-PVP monolayer remained on the polyelectrolyte film, resulting in a pattern of alternating hydrophobic and carboxylic acid containing hydrophilic regions. The surface was used as a template for the selective deposition of TiO2 on the multilayer surface, using an acid-catalyzed hydrolysis of(NH4)2TiF6. Using this novel approach, we have successfully demonstrated the patterning of TiO2 film on a polyelectrolyte multilayer. Finally, nanoscale features consisting of 200 nm lines alternating with a 350 nm period was accomplished. This paper represents the first such attempt to create an all-polymer nonlithographic template for the directed deposition of TiO2 or related metal oxides; this technique, which utilizes the versatile polyelectrolyte multilayer process, enables the construction of complex polymer-inorganic microstructures suitable for electrooptical and photonic applications.     

Permanent gold nanoparticle coatings on polyelectrolyte multilayer modified capillaries for open-tubular capillary electrochromatography

This paper reports on a new strategy to coat fused silica capillaries through ionic adsorption of gold nanoparticles (AuNPs) on a polyelectrolyte multilayer (PEM) modified capillary wall. The coating was constructed in situ by alternating rinses with positively charged poly(diallydimethylammonium chloride), negatively charged poly(sodium-4-styrenesulfonate), and positively charged AuNPs. After self-assembly of n-octadecanethiol onto the surface of AuNPs, the modified capillary was investigated as a new medium for the separation of neutral analytes and proteins in open-tubular capillary electrochromatography (OT-CEC). The surface coverage of the capillary wall was increased using the high density of AuNPs which were dynamically capped with 4-dimethylaminopyridine (DMAP). The chromatographic performance of the column coated with positively charged AuNPs was remarkably improved compared with a column modified with negatively charged AuNPs. The coating was robust over more than 810 runs in this study and also showed high stability against 0.01 M NaOH, 0.01 M HCl, and electrolyte concentrations up to 70 mM. The run-to-run, day-to-day, and capillary-to-capillary reproducibilities of electroosmotic flow were satisfying with relative standard deviation values of less than 1% in all cases. The AuNP-coated PEM modified capillary column not only showed good performance for neutral analytes but also was suitable for the analysis of both basic and acidic proteins.