Motion‐Based,High‐Yielding,and Fast Separation of Different Charged Organics in Water

We report a self‐propelled Janus silica micromotor as a motion‐based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self‐propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s^?1. Biotin‐functionalized Janus micromotors can specifically capture and rapidly transport streptavidin‐modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self‐propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab‐on‐chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications.     

One‐Step Microfluidic Fabrication of Polyelectrolyte Microcapsules in Aqueous Conditions for Protein Release

We report a microfluidic approach for one‐step fabrication of polyelectrolyte microcapsules in aqueous conditions. Using two immiscible aqueous polymer solutions, we generate transient water‐in‐water‐in‐water double emulsion droplets and use them as templates to fabricate polyelectrolyte microcapsules. The capsule shell is formed by the complexation of oppositely charged polyelectrolytes at the immiscible interface. We find that attractive electrostatic interactions can significantly prolong the release of charged molecules. Moreover, we demonstrate the application of these microcapsules in encapsulation and release of proteins without impairing their biological activities. Our platform should benefit a wide range of applications that require encapsulation and sustained release of molecules in aqueous environments.     

A New Approach to Catalyze Template Polymerization of Aniline Using Electrostatically Multilayered Hematin Assemblies

Abstract

In this work, we describe a new approach to catalyze the template polymerization of conducting polyaniline (Pani). Electrostatic layer‐by‐layer (ELBL) self‐assembly of a polyelectrolyte and a biomimetic catalyst, hematin has been utilized to construct a nanocomposite film catalyst. Poly(dimethyl diallylammonium chloride) (PDAC) and hematin have been used as polycation and counter anions, respectively. The absorption spectra by UV‐VIS‐NIR spectroscopy showed that a conductive form Pani was formed, not only as a coating on the surface of the ELBL composites, but was also formed in solution. Furthermore, it was found that the reaction rate was affected by pH and concentration of hematin in the multilayers. The feasibility of controlled desorption of hematin molecules from the LBL assembly was explored and demonstrated by changing pH and hematin concentration. It is believed that hematin sandwiched between positively charged polyelectrolytes in the composite films was slowly released into the solutions and then used to catalyze the template polymerization of aniline with SPS, resulting in a water soluble form of Pani. The polymerization rate of aniline in solution was enhanced with decreasing pH of the solutions due to increased desorption of hematin nanoparticles from the multilayers. These ELBL hematin assemblies demonstrated both a way to functionalize surfaces with conductive Pani and a potential method of reusability of the catalyst for improved cost effectiveness.     

Control of the water permeability of polyelectrolyte multilayers by deposition of charged paraffin particles

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.     

Odd‐even effect during layer‐by‐layer assembly of polyelectrolytes inspired by marine mussel

Biomimetic polyelectrolyte of Dopa modified poly(acrylic acid) (PAADopa) was synthesized taking advantage of Dopa, the major unit of marine adhesive proteins. Zinc crosslinked PAADopa (PAADopa‐Zn) were formed at acidic pH for more compact structure and assembled with the positively charged polyethylenimine (PEI) to build robust polyelectrolyte multilayers at high salt concentration. Effects of pH, crosslinking degree, and salt concentration on polymer structure, film building process, and morphology were investigated, respectively. An “odd‐even” effect was observed by quartz crystal microbalance with dissipation and AFM in the presence of zinc ion, which becomes more obvious with an optimum crosslinking degree (Zn/Dopa = 2.0) under high salt concentration (0.6 M NaCl). It indicates the different swollen properties of PEI chain and PAADopa‐Zn complexes during the layer‐by‐layer building process under optimum crosslinking degree of PAADopa‐Zn at high salt concentration. Such odd‐even phenomenon of the biocompatible system is of critical importance for understanding the mechanism of layer formation and film structures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 245–255     

Formation of polyelectrolyte multilayer architectures with embedded DMPC studied in situ by neutron reflectometry

The coupling of lipid molecules to polymer components in a planar biomimetic model membrane made of a lipid bilayer (dimyristoylphosphatidylcholine) supported by polyelectrolyte multilayers is studied. The polyelectrolyte support was prepared by layer-by-layer deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly(sodium 4-styrenesulfonate) (PSS). Two polymer sample terminations were considered: positively charged (PAH-terminated) and negatively charged (PSS-terminated). Neutron reflectometry studies showed that, whereas positively charged samples did not favor the deposition of lipid, negatively charged samples allowed the deposition of a lipid bilayer with a thickness of approximately 5 nm. In the latter case, formation of polyelectrolyte layers after the deposition of the lipid layer was also possible.     

Layer‐by‐layer assembly of weak‐strong copolymer polyelectrolytes: A route to morphological control of thin films

Multilayer films were assembled from a strong polyelectrolyte (poly(diallyldimethylammonium chloride), PDADMAC) and a copolymer containing both strongly charged styrene sulfonate moieties and weakly charged maleic acid moieties (poly(4‐styrenesulfonic acid‐co‐maleic acid), PSSMA). Growth of PSSMA/PDADMAC multilayers was linear, as characterized by UV‐vis spectroscopy and quartz crystal microgravimetry. The influence of both the pH of the PSSMA adsorption solutions and the ratio of SS:MA in the PSSMA on multilayer properties was investigated. Fourier transform infrared spectroscopy results showed that the ionization of carboxylic acid groups in PSSMA/PDADMAC multilayers did not vary significantly with changes in the PSSMA assembly pH. However, the multilayers showed different thicknesses, surface morphologies, and stability to post‐assembly pH treatment. We also demonstrate that PSSMA/PDADMAC multilayers are significantly more stable than PSSMA/PAH multilayers after post‐assembly pH treatment (i.e. the films remain intact when exposed to pH extremes). In addition, the surface morphology of two films (PSSMA 1:1 assembled at pH 5.8, post‐treated at pH 2 and PSSMA 3:1 assembled at pH 5.8, post‐treated at pH 11) changed significantly when the films were exposed to solutions of different pH and, in the former case, this change in film morphology was reversible. The porous morphology after treatment at pH 2 could be reversed to give a significantly smoother film after subsequent exposure to water for 24 h. Our results demonstrate that by the rational choice of the assembly pH of PSSMA, stable and pH‐responsive films can be obtained via the sequential assembly of PSSMA and PDADMAC. These films have potential in controlled release applications where film stability and pH‐responsive behavior are essential. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4341‐4351, 2007     

Hydration of the Calcium Dication: Direct Evidence for Second Shell Formation from Infrared Spectroscopy

Infrared laser action spectroscopy in a Fourier‐transform ion cyclotron resonance mass spectrometer is used in conjunction with ab initio calculations to investigate doubly charged, hydrated clusters of calcium formed by electrospray ionization. Six water molecules coordinate directly to the calcium dication, whereas the seventh water molecule is incorporated into a second solvation shell. Spectral features indicate the presence of multiple structures of Ca(H₂O)₇²⁺ in which outer‐shell water molecules accept either one (single acceptor) or two (double acceptor) hydrogen bonds from inner‐shell water molecules. Double‐acceptor water molecules are predominately observed in the second solvent shells of clusters containing eight or nine water molecules. Increased hydration results in spectroscopic signatures consistent with additional second‐shell water molecules, particularly the appearance of inner‐shell water molecules that donate two hydrogen bonds (double donor) to the second solvent shell. This is the first reported use of infrared spectroscopy to investigate shell structure of a hydrated multiply charged cation in the gas phase and illustrates the effectiveness of this method to probe the structures of hydrated ions.     

Superparamagnetic pH‐sensitive multilayer hybrid hollow microspheres for targeted controlled release

The superparamagnetic multilayer hybrid hollow microspheres have been fabricated using the layer‐by‐layer assembly technique by the electrostatic interaction between the polyelectrolyte cation chitosan (CS) and the hybrid anion citrate modified ferroferric oxide nanoparticles (Fe₃O₄‐CA) onto the sacrificial polystyrene sulfonate microspheres templates after etching the templates by dialysis. The saturation magnetization and magnetite contents of the superparamagnetic multilayer hybrid hollow microspheres were 32.46 emu/g and 51.3%, respectively. The hybrid hollow microspheres showed pH‐sensitive characteristics. The adsorption and release of the basic dye (methylene blue) were applied to investigate the interaction between the amino groups of CS and the carboxyl groups of the Fe₃O₄‐CA nanoparticles in different pH media. The superparamagnetic pH‐sensitive multilayer hybrid hollow microspheres are expected to be used for the targeted controlled release of drugs or in diagnostics. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3135–3144, 2010     

Stability and structure of polyelectrolyte multilayers deposited from salt free solutions

Molecular-dynamics (MD) simulation results show that polyelectrolyte multilayers deposited from salt free solutions on charged planar surfaces are thermodynamically stable structures that form spontaneously regardless of the method of deposition. The simulation also shows that the polyelectrolyte multilayers are "fuzzy" in nature and molecules in one layer interpenetrate other layers. The influence of chain length, surface charge, and polymer charge is also investigated. Layer thickness was found to be independent of chain length. The ratio of surface to chain charge was found to influence the thickness of the first layer and the amount of polymer absorbed in the first few layers. The thickness of the subsequent layers was found to be independent of the charge ratio.     

Assembly of multilayer films from polyelectrolytes containing weak and strong acid moieties

Multilayer films were assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA), deposited in alternation with poly(allylamine hydrochloride) (PAH). The strongly charged groups (styrene sulfonate, SS) are expected to form electrostatic linkages (to enhance film stability), while the weakly charged groups (maleic acid, MA) can alter multilayer film properties because they are responsive to external pH changes. In this study, we varied several assembly conditions such as pH, SS/MA ratio in PSSMA, and the ionic strength of the polyelectrolyte solutions. The multilayer films were also treated by immersion into pH 2 and 11 solutions after assembly. Quartz crystal microgravimetry and UV-visible spectrophotometry showed that the thickness of PSSMA/PAH multilayers decreases with increasing assembly pH regardless of whether salt was present in the polyelectrolyte solutions. When no salt was added, the multilayers are thinner, smoother, and grow less regularly. Atomic force microscopy images indicate that the presence of salt in polyelectrolyte solutions results in rougher surface morphologies, and this effect is especially significant in multilayers assembled at pH 2 and pH 11. When both polyelectrolytes are adsorbed at conditions where they are highly charged, salt was necessary to promote regular multilayer growth. Fourier transform infrared spectroscopy studies show that the carboxylic acids in the multilayers are essentially ionized when assembled from different pHs in 0.5 M sodium chloride solutions, whereas some carboxylic acids remain protonated in the multilayers assembled from solutions with no added salt. This resulted in different pH stability regimes when the multilayers were exposed to different pH solutions, post assembly.     

Functional artificial free-standing yeast biofilms

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.     

Adsorption of poly(vinyl formamide-co-vinyl amine) onto silica particle surfaces and stability of the formed hybrid materials

In order to produce silica/polyelectrolyte hybrid materials the adsorption of the polyelectrolyte poly(vinyl formamide-co-vinyl amine), P(VFA-co-VAm) was investigated. The adsorption of the P(VFA-co-VAm) from an aqueous solution onto silica surface is strongly influenced by the pH value and ionic strength of the aqueous solution, as well as the concentration of polyelectrolyte. The adsorption of the positively charged P(VFA-co-VAm) molecules on the negatively charged silica particles offers a way to control the surface charge properties of the formed hybrid material. Changes in surface charges during the polyelectrolyte adsorption were studied by potentiometric titration and electrokinetic measurements. X-ray photoelectron spectroscopy (XPS) was employed to obtain information about the amount of the adsorbed polyelectrolyte and its chemical structure. The stability of the adsorbed P(VFA-co-VAm) was investigated by extraction experiments and streaming potential measurements. It was shown, that polyelectrolyte layer is instable in an acidic environment. At a low pH value a high number of amino groups are protonated that increases the solubility of the polyelectrolyte chains. The solvatation process is able to overcompensate the attractive electrostatic forces fixing the polyelectrolyte molecules on the substrate material surface. Hence, the polyelectrolyte layer partially undergoes dissolving process.     

Interactions of Water‐Soluble Poly(sodium 4‐styrenesulfonate) with Iminodiacetic Acid and Cu2+

The multicomponent system consisting of poly(sodium 4‐styrenesulfonate) (PSS), iminodiacetic acid (IDAA), and Cu(NO₃)₂ in water at pH 4 was studied by means of ultrafiltration at low and relatively high ionic strengths. Under the experimental conditions, IDAA is negatively charged, and is slightly retained in ultrafiltration experiments in the presence of the water‐soluble polyelectrolyte PSS. The positively charged copper ions are strongly retained by PSS. Due to the capability of IDAA to form stable complexes with Cu²⁺ ions, the resulting blue 1:1 complex between IDAA and Cu²⁺ is not retained by PSS, but is eluted from the ultrafiltration cell at pH 4.     

Entrapment of α‐Chymotrypsin into Hollow Polyelectrolyte Microcapsules

Stable hollow polyelectrolyte capsules were produced by the layer‐by‐layer assembling of non‐biodegradable polyelectrolytes – poly(allylamine) and poly(styrenesulfonate) on melamine formaldehyde microcores followed by the core decomposition at low pH. A proteolytic enzyme, α‐chymotrypsin, was encapsulated into these microcapsules with high yields of up to 100%. The encapsulation procedure was based on the protein adsorption onto the capsule shells and on the pH‐dependent opening and closing of capsule wall pores. The protein in the capsules retained a high activity, and thermo‐ and storage stability. The nanostructured polyelectrolyte shell protected the proteinase from a high molecular weight inhibitor. Such enzyme‐loaded capsules can be used as microreactors for biocatalysis.     

pH‐Disintegrable Polyelectrolyte Multilayer‐Coated Mesoporous Silica Nanoparticles Exhibiting Triggered Co‐Release of Cisplatin and Model Drug Molecules

We report on the fabrication of pH‐disintegrable polyelectrolyte multilayer‐coated mesoporous silica nanoparticles (MSN) capable of triggered co‐release of cisplatin and model drug molecules. The outer polyelectrolyte multilayer was assembled from permanently cationic polyelectrolyte, poly(allyl amine hydrochloride) (PAH), and negatively charged polyelectrolyte, P(DMA‐co‐TPAMA), consisting of N,N‐dimethylacrylamide (DMA) and 3,4,5,6‐tetrahydrophthalic anhydride‐functionalized N‐(3‐aminopropyl)methacrylamide (TPAMA) monomer units, which exhibits pH‐induced charge conversion characteristics. Thus, the subtle alteration of solution pH from 7.4 to ≈5–6 can lead to the disintegration of outer polyelectrolyte multilayers, accompanied with the co‐release of cisplatin and RhB.

     

Nanoporous platinum solid-state reference electrode with layer-by-layer polyelectrolyte junction for pH sensing chip

A novel solid-state reference electrode was developed by combining nanoporous Pt with polyelectrolyte junction. The polyelectrolyte junction was formed in the microchannel connecting the nanoporous Pt and the sample solution, and had layer-by-layer structure of oppositely charged polyelectrolytes. The layer-by-layer polyelectrolyte junction effectively blocked the mass transport of ions and maintains constant pH environments on the surface of the nanoporous Pt. The assembly of the polyelectrolyte junction and the nanoporous Pt, which produced reportedly a stable open-circuit potential in response to constant pH, exhibited outstanding performance as a solid-state reference electrode (e.g., excellent reproducibility of ±4 mV (n = 5), good long term stability of ±1 mV (for 50 h), and independence of solution environments like pH and ionic strength). A working principle of the solid-state reference electrode with layer-by-layer polyelectrolyte junction was suggested in terms of the roles of each layer and the effect of the neighboring layer. As a demonstrative application of the solid-state reference electrode, a miniaturized chip-type solid-state pH sensor comprised of two nanoporous Pt electrodes and a micro-patterned layer-by-layer polyelectrolyte junction was developed. The solid-state pH sensing chip showed reliable pH responses without liquid junction and successfully worked in a variety of buffers, beverages, and biological samples, showing its potential utility for practical applications. In addition, the solid-state pH sensing chip was integrated in a microfluidic system to be utilized for pH monitoring in microfluidic flow.     

Heterostructured magnetic nanotubes

Heterostructured magnetic tubes with submicrometer dimensions were assembled by the layer-by-layer deposition of polyelectrolytes and nanoparticles in the pores of track-etched polycarbonate membranes. Multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) assembled at high pH (pH > 9.0) were first assembled into the pores of track-etched polycarbonate membranes, and then multilayers of magnetite (Fe3O4) nanoparticles and PAH were deposited. Transmission electron microscopy (TEM) confirmed the formation of multilayer nanotubes with an inner shell of magnetite nanoparticles. These tubes exhibited superparamagnetic characteristics at room temperature (300 K) as determined by a SQUID magnetometer. The surface of the magnetic nanotubes could be further functionalized by adsorbing poly(ethylene oxide)-b-poly(methacrylic acid) block copolymers. The separation and release behavior of low molecular weight anionic molecules (i.e., ibuprofen, rose bengal, and acid red 8) by/from the multilayer nanotubes were studied because these tubes could potentially be used as separation or targeted delivery vehicles. The magnetic tubes could be successfully used to separate (or remove) a high concentration of dye molecules (i.e., rose bengal) from solution by activating the nanotubes in acidic solution. The release of the anionic molecules in physiologically relevant buffer solution showed that whereas bulky molecules (e.g., rose bengal) release slowly, small molecules (i.e., ibuprofen) release rapidly from the multilayers. The combination of the template method and layer-by-layer deposition of polyelectrolytes and nanoparticles provides a versatile means to create functional nanotubes with heterostructures that can be used for separation as well as targeted delivery.     

Competing mechanisms in polyelectrolyte multilayer formation and swelling: Polycation–polyanion pairing vs. polyelectrolyte–ion pairing

The competition of interactions between charged groups of polyanions and polycations and their interaction with small counterions strongly affect the formation and stability of polyelectrolyte multilayers. This has consequences for the properties of polyelectrolyte multilayers like mechanics, polymer mobility and swelling in water.     

Molecular dynamics simulations of polyelectrolyte multilayering on a charged particle

Molecular dynamics simulations of polyelectrolyte multilayering on a charged spherical particle revealed that the sequential adsorption of oppositely charged flexible polyelectrolytes proceeds with surface charge reversal and highlighted electrostatic interactions as the major driving force of layer deposition. Far from being completely immobilized, multilayers feature a constant surge of chain intermixing during the deposition process, consistent with experimental observations of extensive interlayer mixing in these films. The formation of multilayers as well as the extent of layer intermixing depends on the degree of polymerization of the polyelectrolyte chains and the fraction of charge on its backbone. The presence of ionic pairs between oppositely charged macromolecules forming layers seems to play an important role in stabilizing the multilayer film.