Electrostatic cross-linking-induced self-assembly of poly(allylamine hydrochloride) using Allura Red AC

The self-assembly of poly(allylamine hydrochloride) (PAH) through electrostatic cross-linking using Allura Red AC (AR) was explored in an aqueous solution. PAH showed no self-assembly in the absence of AR. A light-scattering study demonstrated that PAH formed aggregates of ca. 300-nm diameter by the addition of AR at 0.1 of the molar ratio of the SO₃Na unit of AR to NH₃Cl of PAH (SO₃Na/NH₃Cl). The PAH diameter decreased as the SO₃Na/NH₃Cl ratio increased up to 0.5 and thereafter rapidly increased due to sedimentation of the aggregates. The analysis of the normalized time correlation function of the scattered field confirmed that the electrostatic cross-linking by AR provided polydispersed aggregates of PAH. The UV analysis revealed that the PAH self-assembly caused a blue shift of AR. The size of the aggregates was independent of the PAH concentration. On the other hand, the aggregate size was strongly dependent on the temperature.     

Adsorption of Cationic Laser Dye onto Polymer/Surfactant Complex Film

Fabrication of complex molecular films of organic materials is one of the most important issues in modern nanoscience and nanotechnology. Soft materials with flexible properties have been given much attention and can be obtained through bottom up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and technologies. In this work, we report the successful incorporation of cationic laser dye rhodamine 6G abbreviated as R6G into the pre-assembled polyelectrolyte/surfactant complex film onto quartz substrate by electrostatic adsorption technique. Poly(allylamine hydrochloride) (PAH) was used as polycation and sodium dodecyl sulphate (SDS) was used as anionic surfactant. UV-Vis absorption spec-troscopic characterization reveals the formation of only H-type aggregates of R6G in their aqueous solution and both H- and J-type aggregates in PAH/SDS/R6G complex layer-by-layber films as well as the adsorption kinetics of R6G onto the complex films. The ratio of the absorbance intensity of two aggregated bands in PAH/SDS/R6G complex films is merely independent of the concentration range of the SDS solution used to fabricate PAH/SDS com-plex self-assembled films. Atomic force microscopy reveals the formation of R6G aggregates in PAH/SDS/R6G complex films.     

Optical Gas Sensor Fabrication Based on Porphyrin-Anchored Electrostatic Self-Assembly onto Tapered Optical Fibers

Tapered optical fibers with nano-assembled coatings of thicknesses of order tens of nanometres were used for the detection of ammonia gas. The film coating was composed of alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) and poly(allylamine hydrochloride) (PAH), which were deposited using the electrostatic self-assembly process (ESA). Exposure of a PAH/TSPP nano-assembled non-adiabatic tapered optical fiber with a waist diameter of 10 µm to ammonia induced significant optical changes in the transmission spectrum of the optical fiber. The fiber optic sensor showed a linear sensitivity to the concentration of ammonia in the range of 10–100 ppm, with response and recovery times less than 100 and 240 sec, respectively. The 3σ limit of detection (LOD) was estimated to be ca. 2 ppm.     

Directed Self-assembly of Vertical PS-b-PMMA Nanodomains Grown on Multilayered Polyelectrolyte Films

Layer-by-layer polyelectrolyte self-assembly, a common method for preparing high-quality ultra-thin films, was employed to direct the self-assembly behavior of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) block copolymer for the first time. Differing from the previous neutral polymer brushes anchored to silicon substrates via chemical modification, polyelectrolyte multilayers(PEMs) were anchored by electrostatic interaction and provided a stable, smooth, and neutral interface. In the present study, PS-b-PMMA was deposited on poly(acrylamide hydrochloride)/poly(acrylic acid)(PAH/PAA) PEMs prepared by layer-by-layer self-assembly to successfully yield vertical nanodomains after thermal annealing. Seven layered PEMs revealed an excellent, smooth surface, with a low roughness of 0.6 nm. The periodic structure with interlamellar spacing of 47 nm was determined by grazing-incidence small-angle X-ray scattering(GISAXS). The morphology of the PS-b-PMMA nanodomains depended on the polyanion-to-polycation concentration ratio, which is related to the interaction between the block copolymer and the substrate. Our results demonstrate that layer-by-layer self-assembly is a helpful method for the phase separation of block polymers and the fabrication of vertical, ordered nanodomains.     

Preparation and characterization of an anionic dye-polycation molecular films by electrostatic layer-by-layer adsorption process

This communication reports the formation and characterization of self-assembled films of a low molecular weight anionic dye amaranth and polycation poly(allylamine hydrochloride) (PAH) by electrostatic alternating layer-by-layer (LBL) adsorption. It was observed that there was almost no material loss occurred during adsorption process. The UV-vis absorption and fluorescence spectra of amaranth solution reveal that with the increase in amaranth concentration in solution, the aggregated species starts to dominate over the monomeric species. New aggregated band at 600 nm was observed in amaranth-PAH mixture solution absorption spectrum. A new broad low intense band at the longer wavelength region, in the amaranth-PAH mixture solution fluorescence spectrum was observed due to the closer association of amaranth molecule while tagged into the polymer backbone of PAH and consequent formation of aggregates. The broad band system in the 650-750 nm region in the fluorescence spectra of different layered LBL films changes in intensity distribution among various bands within itself, with changing layer number and at 10 bilayer LBL films the longer wavelength band at 710 nm becomes prominent. Existence of dimeric or higher order n-meric species in the LBL films was confirmed by excitation spectroscopic studies. Almost 45 min was required to complete the interaction between amaranth and PAH molecules in the one-bilayer LBL film.     

Layer-by-layer self-assembled ultrathin multilayer films of lanthanide polyoxometalates and poly(allylamine hydrochloride) and their photoluminescent properties

Ultrathin multilayer films of two lanthanide polyoxometalates (LPOMs), K(17)[Eu(P(2)W(17)O(61))(2)] (EPW) and K(13)[Eu(SiW(11)O(39))(2)] (ESW), and poly(allylamine hydrochloride) (PAH) have been prepared by layer-by-layer self-assembly from dilute aqueous solutions. UV-vis spectroscopy and ellipsometry respectively show that the absorbance values at characteristic wavelengths and the thicknesses of the multilayer films increase linearly with the number of LPOM/PAH bilayers, suggesting that the deposition process is linear and highly reproducible from layer to layer. Average thicknesses of ca. 3.4 and 2.4 nm were determined for the EPW/PAH and ESW/PAH bilayers by ellipsometry, respectively. In addition, scanning electron microscopy (SEM) and atomic force microscopy (AFM) images provide the surface morphology of the LPOM/PAH films, indicating that the film surface is relatively uniform and smooth. The photoluminescent properties of these films have also been investigated by fluorescence spectroscopy. The LPOM/PAH multilayer film has a good thermal stability as shown by UV-vis, X-ray photoelectron, and fluorescence spectra.     

Insulin Delivery from Glucose-Responsive,Self-Assembled,Polyamine Nanoparticles: Smart “Sense-and-Treat” Nanocarriers Made Easy

Polyamine–salt aggregates (PSA) are biomimetic soft materials that have attracted great attention due to their straightforward fabrication methods, high drug-loading efficiencies, and attractive properties for pH-triggered release. Herein, a simple and fast multicomponent self-assembly process was used to construct cross-linked poly(allylamine hydrochloride)/phosphate PSAs (hydrodynamic diameter of 360 nm) containing glucose oxidase enzyme, as a glucose-responsive element, and human recombinant insulin, as a therapeutic agent for the treatment of diabetes mellitus (GI-PSA). The addition of increasing glucose concentrations promotes the release of insulin due to the disassembly of the GI-PSAs triggered by the catalytic in situ formation of gluconic acid. Under normoglycemia, the GI-PSA integrity remained intact for at least 24 h, whereas hyperglycemic conditions resulted in 100 % cargo release after 4 h of glucose addition. This entirely supramolecular strategy presents great potential for the construction of smart glucose-responsive delivery nanocarriers.     

Electrostatic long-range and short-range interactions in linear poly(allylamine hydrochloride) chains

The efficiencies of two azo initiators in the polymerization of allylamine salts in water and organic solvents were compared. The hydrodynamic and molecular characteristics of poly(allylamine hydrochloride) in 0.1 M NaCl in the molecular mass range M×10^?3=18?65 were studied, and the scaling relationships were derived for the intrinsic viscosity ([η]=7.65×10^?3 M ^0.8±0.1), translational diffusion coefficient (D ₀=2.41×10^?4 M ^{?(0.59±0.05)}), and velocity sedimentation coefficient (s ₀=2.77×10^?15 M ^0.41±0.05). The hydrodynamic data were interpreted in terms of electrostatic long-range and short-range interactions. The equilibrium rigidity of poly(allylamine hydrochloride) chains in 0.1 M NaCl and its structural and electrostatic constituents were quantitatively estimated. It was shown that the conformation of poly(allylamine hydrochloride) chains in pure water is close to rodlike.     

Grafted ionomer complexes and their effect on protein adsorption on silica and polysulfone surfaces

We have studied the formation and the stability of ionomer complexes from grafted copolymers (GICs) in solution and the influence of GIC coatings on the adsorption of the proteins β-lactoglobulin (β-lac), bovine serum albumin (BSA), and lysozyme (Lsz) on silica and polysulfone. The GICs consist of the grafted copolymer PAA₂₈-co-PAPEO₂₂ {poly(acrylic acid)-co-poly[acrylate methoxy poly(ethylene oxide)]} with negatively charged AA and neutral APEO groups, and the positively charged homopolymers: P2MVPI₄₃ [poly(N-methyl 2-vinyl pyridinium iodide)] and PAH?HCl₁₆₀ [poly(allylamine hydrochloride)]. In solution, these aggregates are characterized by means of dynamic and static light scattering. They appear to be assemblies with hydrodynamic radii of 8 nm (GIC-PAPEO₂₂/P2MVPI₄₃) and 22 nm (GIC-PAPEO₂₂/PAH?HCl₁₆₀), respectively. The GICs partly disintegrate in solution at salt concentrations above 10 mM NaCl. Adsorption of GICs and proteins has been studied with fixed angle optical reflectometry at salt concentrations ranging from 1 to 50 mM NaCl. Adsorption of GICs results in high density PEO side chains on the surface. Higher densities were obtained for GICs consisting of PAH?HCl₁₆₀ (1.6?÷?1.9 chains/nm²) than of P2MVPI₄₃ (0.6?÷?1.5 chains/nm²). Both GIC coatings strongly suppress adsorption of all proteins on silica (>90%); however, reduction of protein adsorption on polysulfone depends on the composition of the coating and the type of protein. We observed a moderate reduction of β-lac and Lsz adsorption (>60%). Adsorption of BSA on the GIC-PAPEO₂₂/P2MVPI₄₃ coating is moderately reduced, but on the GIC-PAPEO₂₂/PAH?HCl₁₆₀ coating it is enhanced.     

Probe diffusion from dilute to concentrated in polyelectrolyte solution: salt effect

The adsorption behaviors between a positively charged poly(allyamine) hydrochloride (PAH) matrix and negatively charged sulfate polystyrene (PS) particle probe were investigated using dynamic light scattering (DLS) and fluorescence photobleaching recovery (FPR) with reference to the matrix and salt concentration. The system experienced a steep decrease of diffusion (flocculation) under dilute conditions and a gradual decrease above semidilute concentrations. The fluorescence photobleaching recovery and viscometry experiments revealed that the probe behaviors in the polyelectrolyte solution were strongly affected by the coil overlap concentration (0.5 g/L poly(allyamine) hydrochloride). Near the coil overlap concentration, the hydrodynamic radius representing the entanglement dimension of the matrix was approximately 30 nm; however, at higher concentrations the radius gradually decreased, suggesting a transition toward a network structure. In this system, the salt performed two roles: (1) reinforcing the electrostatic interaction, and (2) preventing electrostatic interaction between the probe and the matrix.     

Micellar Behavior of Polystyrene-Poly(Ethylene Oxide) Diblock Copolymers in Aqueous Media: Effect of Copolymer Composition,Temperature, Salt,and Surfactants

Formation and structure of micelles from two amphiphilic polystyrene-block-poly(ethylene oxide) (PS-PEO) diblock copolymers (PS mol.wt. 1000; PEO mol.wt. 3000 and 5000) were examined by surface tension, viscosity, steady state fluorescence, dynamic light scattering (DLS), small angle neutron scattering (SANS), and cryo-transmission electron microscopy (cryo-TEM). The critical micelle concentration (CMC) of the copolymers in aqueous solution was ca. 0.05%; micelle hydrodynamic diameter was 30–35 nm with a narrow size distribution. SANS studies show that the copolymers form ellipsoidal micelles with semi major axis ～23 nm and semi minor axis ～8 nm. No significant change in the structure was found with temperature and presence of salt. The copolymer micelles interaction with the ionic surfactants sodium dodecyl sulphate (SDS) and dodecyltrimethylammonium bromide (DTAB) was also examined by DLS and SANS.     

Magnetic switch of permeability for polyelectrolyte microcapsules embedded with Co@Au nanoparticles

We explored using a magnetic field to modulate the permeability of polyelectrolyte microcapsules prepared by layer-by-layer self-assembly. Ferromagnetic gold-coated cobalt (Co@Au) nanoparticles (3 nm diameter) were embedded inside the capsule walls. The final 5 mum diameter microcapsules had wall structures consisting of 4 bilayers of poly(sodium styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH), 1 layer of Co@Au, and 5 bilayers of PSS/PAH. External alternating magnetic fields of 100-300 Hz and 1200 Oe were applied to rotate the embedded Co@Au nanoparticles, which subsequently disturbed and distorted the capsule wall and drastically increased its permeability to macromolecules like FITC-labeled dextran. The capsule permeability change was estimated by taking the capsule interior and exterior fluorescent intensity ratio using confocal laser scanning microscopy. Capsules with 1 layer of Co@Au nanoparticles and 10 polyelectrolyte bilayers are optimal for magnetically controlling permeability. A theoretical explanation was proposed for the permeability control mechanisms. "Switching on" of these microcapsules using a magnetic field makes this method a good candidate for controlled drug delivery in biomedical applications.     

含乳糖聚电解质靶向微胶囊的层层自组装构筑

设计合成了己二酸乳糖乙烯酯/对苯乙烯磺酸钠共聚物（PLESS）,通过层层自组装技术构筑聚烯丙基胺盐酸盐（PAH）与含乳糖聚电解质PLESS的靶向微胶囊。以紫外-可见吸收光谱监测了PAH与PLESS在平面的石英片进行层层自组装过程,研究了不同实验条件（聚电解质浓度、溶液盐度、盐种类）对PAH/PLESS多层膜自组装的影响;PAH与PLESS在球形碳酸钙微球模板上层层自组装,去除模板后得到层状结构的微胶囊,用透射电镜（TEM）等方法观察其形态形貌;通过花生凝集素识别考察其潜在靶向性;通过细胞MTT活性试验评价其生物相容性。     

Nanoparticle-assembled capsule synthesis: formation of colloidal polyamine-salt intermediates

There is current interest in developing new synthesis strategies for multifunctional hollow spheres with tunable structural properties that would be useful in encapsulation and controlled release applications. A new route was reported recently, in which the sequential reaction of polyamines, multivalent anions, and charged nanoparticles leads to the formation of polymer-filled and water-filled organic/inorganic micron-sized structures known as nanoparticle-assembled capsules. This technique is unique among other capsule preparation routes, as it allows the rapid and scalable formation of robust shells at room temperature, in near-neutral water, and with readily available precursors. This nanoparticle assembly synthesis route involves two steps: the formation of polymer aggregates and the subsequent deposition of particles around the aggregates. The purpose of this paper is to understand in greater detail the noncovalent chemistry of the polymer-salt aggregation step. With poly(allylamine hydrochloride) (PAH) as the model polymer, aggregate formation was investigated as a function of charge ratio, pH, and time through dynamic light scattering, electrophoretic mobility measurements, chloride ion measurements, and optical microscopy. PAH formed aggregates by the cross-linking action of divalent and higher-valent anions above a critical charge ratio and in a pH range defined by the pKa values of PAH and the anion. The aggregates grew in size through coalescence and with growth rates that depended on their surface charge. Controlling polymer aggregate growth provided a direct and simple means to adjust the size of the resultant capsule materials.     

Self-assembly of poly(ethylene oxide)-block-poly(acrylic acid) induced by CaCl2: mechanistic study

The interaction between CaCl 2 and double hydrophilic block copolymer, poly(ethylene oxide) 45- block-poly(acrylic acid) 70, PEO 45- b-PAA 70, was investigated. At a stoichiometric ratio of Ca2+:COO (-) = 0.5, Ca2+ ions were bound to COO (-) groups on PAA segments via electrostatic interaction. Small particles of 4-8 nm in diameter were observed, suggesting the formation of coil-like polymeric globule induced by charge neutralization. At Ca2+:COO (-) >or= 2.5, monodispersed aggregates of average hydrodynamic diameter of 52.0 +/- 7.4 nm were produced. The ISE, ITC, surface tension and fluorescence spectroscopic data confirmed that the formation of these aggregates is not the result of interaction between excess Ca2+ ions and the polymer, but rather it is due to changes in the water activity that triggers the structural rearrangement of Ca2+/PEO 45- b-PAA 70 complex.     

Layer-by-layer Multilayer Films Self-assembled from a Rare-earth-containing Poly-oxometalate Na_9[Eu(W_5O_(18))_2] and Poly(allylamine hydrochloride) and Their Photoluminescent Properties

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Decomposition‐Assembly of Tetraphenylethylene Nanoparticles With Uniform Size and Aggregation‐Induced Emission property

Tetraphenylethylene (TPE)‐substituted poly(allylamine hydrochloride) (PAH‐g‐TPE) is synthesized by a Schiff base reaction between PAH and TPE‐CHO. The PAH‐g‐TPE forms micelles in water at pH 6, which are further transformed into pure TPE‐CHO nanoparticles (NPs) with a diameter of ≈300 nm after incubation in a solution of low pH value. In contrast, only amorphous precipitates are obtained when TPE‐CHO methanol solution is incubated in water. The aggregation‐induced emission feature of the TPE molecule is completely retained in the TPE NPs, which can be internalized into cells and show blue fluorescence. Formation mechanism of the TPE NPs is proposed by taking into account the guidance effect of linear and charged PAH molecules, and the propeller‐stacking manner between the TPE‐CHO molecules.     

The impact of the cononsolvency effect on poly (N-isopropylacrylamide) based microgels at interfaces

The paper addresses the effect of solid interfaces on the cononsolvency effect for poly(N-iso propylacrylamide) based microgels containing different contents of the co-monomer allyl acetic acid (AAA). The cononsolvency effect is studied by dynamic light scattering (DLS) in solution and with atomic force microscopy (AFM) at surfaces against different mixtures of water and organic solvent (ethanol, iso-propanol, and tetrahydrofuran). For the studies at interfaces, the microgels are spin coated on silicon wafers that are precoated with poly(allylamine hydrochloride) (PAH). The minimum in particle volume due to cononsolvency shows a pronounced shift from 10–20 % of organic solvent to 40–50 % after deposition at the Si/PAH wafer. The strong shift indicates an increase of water to organic solvent ratio within the gel at the surface with respect to the bulk solution. In order to understand the increase of water to organic solvent ratio, shrinking/reswelling AFM experiments for different spin-coating conditions and under ambient conditions are carried out. Spin coating from water instead from different solvent mixtures has no effect on the cononsolvency. In ambient conditions, the cononsolvency effect disappears     

Manipulating the properties of coacervated polyelectrolyte microcapsules by chemical crosslinking

The properties of coacervated sodium poly(styrene sulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) microcapsules were manipulated by glutaraldehyde crosslinking at mild conditions. Although the crosslinking took place only between the PAH component, only 10% of PSS was lost from the 2-h crosslinked microcapsules. Significant variation in terms of capsule morphology, diameter, and wall thickness was not found by scanning electron microscopy and scanning force microscopy. Although all the microcapsules were not affected by annealing at 70 °C and incubation in 0.1 M HCl for 2 h, the crosslinked microcapsules indeed showed strong ability to resist osmotic-induced capsule invagination. Also, the 20-min and 2-h crosslinked capsule walls have elasticity modulii of 166 and 200 MPa, respectively, which are both larger than that of the original one (140 MPa). The crosslinked microcapsules also showed good stability in 0.01 M NaOH solution and poorer permeability for a large fluorescent probe.     

Compact microcubic structures platform based on self-assembly Prussian blue nanoparticles with highly tuneable conductivity

Control of molecular and supramolecular properties is used to obtain a new advanced hybrid material based on Prussian blue nanoparticles (PB NPs). This hybrid material is obtained through a self-assembled Layer-by-Layer (LbL) approach combining the advantageous features of β-cyclodextrin (β-CD) polysaccharides, PB NPs and poly(allylamine hydrochloride) from electrostatic interaction between the deposited layers. Transmission electronic microscopy images suggested that PB NPs were protected by β-CD polysaccharides that prevent the aggregation phenomena. In addition, as confirmed by scanning electronic microscopy images, it was found that PB NPs are organized in microcubic supramolecular like structures via a mesoscale self-assembly process. Interestingly, the 3-bilayer {PAH/PB-CD} film exhibited a higher density of microcubic structures and a high electrochemical response with PB sites available for redox reactions at a supramolecular level. By utilizing fewer bilayers and consequently less material deposition, the formed {PAH/PB-CD} multilayer films of a tuneable conductivity can be expected to have interesting future applications for host-guest like dependent electrochemical biosensing designs.