John E. Wong

Dual-stimuli responsive PNiPAM microgel achieved via layer-by-layer assembly: Magnetic and thermoresponsive

We describe the synthesis, characterisation and surface-modification of magnetic nanoparticles and a poly(N-isopropylacrylamide) microgel, followed by the assembly and characterisation of magnetic nanoparticles on the microgel. To facilitate this deposition, the surface of the microgel is first modified via the layer-by-layer assembly of polyelectrolytes. One advantage of this concept is that it allows an independent optimization and fine tuning of the magnetic and thermoresponsive properties of individual components (nanoparticles and microgels) before assembling them so that the hybrid core-shell structure retains all the individual properties. The decisive parameter when exploiting the thermoresponsive and magnetic properties in such hybrid core-shell structures is the amount of heat transfer from the magnetic core onto the thermosensitive (loaded) microgel (for the subsequent heat-triggered release of drugs). Inductive heat study reveals that the heat generated by the magnetic nanoparticles is sufficient to cause the collapse of the microgel above its volume phase transition temperature. Successful confinement of positively and negatively charged magnetic nanoparticles between polyelectrolyte layers is achieved using the layer-by-layer deposition onto the microgel. Dynamic light scattering measurements show (i) the presence of each layer successfully deposited, (ii) the preservation of thermoresponsivity in the coated microgel, and (iii) that the magnetic nanoparticles do not get detached during the phase transition of the microgel. Electrophoresis measurements confirm charge reversal at every stage of layering of polycations, polyanions and magnetic nanoparticles. This unique combination of thermoresponsivity and magnetism opens up novel perspectives towards remotely controlled drug carriers.

Specific ion versus electrostatic effects on the construction of polyelectrolyte multilayers.

Self-assembled multilayers of a strong polyanion, poly(sodium 4-styrenesulfonate) (PSS), and a strong polycation, poly[(diallyl-dimethyl-ammonium chloride)-stat-(N-methyl-N-vinyl acetamide)] (P(DADMAC-stat-NMVA)), are fabricated on silicon substrates. This article addresses the effect of electrostatics versus ion specificity. Therefore, multilayer formation and growth are investigated as a function of the charge density of the polycation, the type of salt in the polyelectrolyte dipping solution, and its ionic strength. This study focuses on monovalent ions (Li(+), Na(+), K(+), Cs(+), Rb(+), F(-), Cl(-), Br(-), and ClO(3)(-)). Ellipsometry and X-ray reflectometry data indicate that anions have a significantly larger effect on the thickness of the multilayer, but contrary to other studies on ion-specific effects, the influence of the type of cation is not negligible at higher salt concentrations. Larger ions, with smaller hydration shells, are highly polarizable and consequently interact strongly with charged polyelectrolytes, resulting in thicker and rougher multilayers. AFM studies confirm a higher roughness of the multilayer prepared from larger anions. The substrate can mask ion-specific effects over a distance of about 10 nm. Ion-specific effects become important above an ionic strength of 0.1 M in the case of anions and above an ionic strength of 0.25 M for cations. At lower ionic strengths, electrostatic interactions between and within the polyelectrolyte chains are dominating. Reducing the degree of polymer charge down to 75% does not shift this threshold of ionic strength. It is shown that a combination of ionic strength, polymer charge, and type of ion is a suitable tool for tuning the mobility and stability of polyelectrolyte multilayers.

Layer-by-Layer Modification of Cation Exchange Membranes Controls Ion Selectivity and Water Splitting

The present study investigates the possibility of inducing monovalent ion permselectivity on standard cation exchange membranes, by the layer-by-layer (LbL) assembly of poly(ethyleneimine) (PEI)/poly(styrenesulfonate) (PSS) polyelectrolyte multilayers. Coating of the (PEI/PSS)N LbL multilayers on the CMX membrane caused only moderate variation of the ohmic resistance of the membrane systems. Nonetheless, the polyelectrolyte multilayers had a substantial influence on the monovalent ion permselectivity of the membranes. Permselectivity comparable to that of a commercial monovalent-ion-permselective membrane was obtained with only six bilayers of polyelectrolytes, yet with significantly lower energy consumption per mole of Na(+) ions transported through the membranes. The monovalent ion permselectivity stems from an increased Donnan exclusion for divalent ions and hydrophobization of the surface of the membranes concomitant to their modification. Double-layer capacitance obtained from impedance measurements shows a qualitative indication of the divalent ion repulsion of the membranes. At overlimiting current densities, water dissociation occurred at membranes with PEI-terminated layers and increased with the number of layers, while it was nearly absent for the PSS-terminated layers. Hence, LbL layers allow switching on and turning off water splitting at the surface of ion exchange membranes.

Study of Layer-by-Layer Films on Thermoresponsive Nanogels Using Temperature-Controlled Dual-Focus Fluorescence Correlation Spectroscopy

While a few studies have reported on the layer-by-layer (LbL) assembly of polyelectrolytes on soft and porous templates, none have really demonstrated direct proof that the layers are actually on the template. Thermoresponsive nanogels present challenges that render a quantitative proof of successful polyelectrolyte deposition extremely difficult. Additionally, the fate of the polyelectrolyte has never been investigated during the phase transition of the coated nanogel. Here, the auto- and cross-correlation functions of a labeled polyelectrolyte assembled via the LbL technique onto soft and porous thermoresponsive labeled nanogels using dual-focus fluorescence correlation spectroscopy (2f-FCS) are presented. Performing 2f-FCS as a function of temperature, hydrodynamic radii of nanogels coated with various numbers of layers are determined, which are found to be in excellent agreement with values obtained from dynamic light scattering. This study presents irrefutable quantitative evidence of successful LbL assembly on thermoresponsive nanogels and demonstrates that the layers are not stripped off during the phase transition of the nanogels. Forster Resonance Energy Transfer (FRET) detection also supports our findings.

Surface Modification of Thermoresponsive Microgels via Layer-by-Layer Assembly of Polyelectrolyte Multilayers

This study describes the layer-by-layer (LbL) assembly of polyelectrolyte multilayers of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrenesulfonate) (PSS) on soft and porous supports as provided by the entangled mesh network of poly(N-isopropylacrylamide) (PNiPAM) microgels with varying thermoresponsive core and core-shell structures. Dynamic light scattering was used to follow the build-up of the PDADMAC/PSS multilayer assembly on thermoresponsive microgel particles and electrophoresis measurements were used to confirm charge reversal after each layer deposition. We demonstrate an “odd-even” effect of the size of the coated microgel depending on the type of polyelectrolytes in the outermost layer. We also show that a priming layer of polyethyleneimine (PEI) causes drastic surface modification of the microgel, but that on subsequent adsorption of the next layer (PSS) the thermoresponsive behavior of the native microgel can be recovered. Similarities and differences to LbL assembly of polyelectrolyte multilayers on hard and rigid supports will be discussed.

Polyelectrolyte coating of iron oxide nanoparticles for MRI-based cell tracking

UNLABELLED Iron oxide-based magnetic nanoparticles (MNPs) offer unique properties for cell tracking by magnetic resonance imaging (MRI) in cellular immunotherapy. In this study, we investigated the uptake of chemically engineered NPs into antigen-presenting dendritic cells (DCs). DCs are expected to perceive MNPs as foreign antigens, thus exhibiting the capability to immunologically sense MNP surface chemistry. To systematically evaluate cellular uptake and T2/T2(⁎) MR imaging properties of MNPs, we synthesized polymer-based MNPs by employing layer-by-layer (LbL) technology. Thereby, we achieved modification of particle shell parameters, such as size, surface charge, and chemistry. We found that subcellular packaging of MNPs rather than MNP content in DCs influences MR imaging quality. Increased local intracellular electron density as inferred from transmission electron microscopy (TEM) strongly correlated with enhanced contrast in MRI. Thus, LbL-tailoring of MNP shells using polyelectrolytes that impact on uptake and subcellular localization can be used for modulating MR imaging properties. FROM THE CLINICAL EDITOR In this study, layer-by-layer tailoring of magnetic NP shells was performed using polyelectrolytes to improve uptake by dendritic cells for cell-specific MR imaging. The authors conclude that polyelectrolyte modified NP-s can be used for modulating improving MR imaging quality by increasing subcellular localization.

Catalytic Polyelectrolyte Multilayers at the Bipolar Membrane Interface

Bipolar membranes are laminated anion and cation exchange membranes that split water at their interface very efficiently upon application of an electric field. This paper investigates the layer-by-layer (LbL) deposition of polyelectrolyte multilayers, as a tool to introduce molecularly thin catalyst groups at this interface of bipolar membranes. The bipolar membranes were prepared by first modifying an anion exchange membrane by consecutive dipping LbL assembly, then casting a thin highly charged intermediate layer followed by casting a cation exchange layer. The results reveal that polyelectrolytes of higher charge density coated on the anion exchange layer yield better performance. Several parameters of the LbL interface deposition were varied. Out of the investigated LbL assembly parameters, ionic strength and number of layers have shown the largest influence on catalytic activity as well as ionic selectivity. The membrane with two bilayers of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) and poly(ethyleneimine) (PEI), where the PEI was prepared in 0.5 M NaCl, gave rise to the best performance. Surprisingly, detailed data analysis at low electrical potential suggests that the interface layers of a bipolar membrane play a major role in its permselectivity. Previously, only the bulk thickness of the anion and cation exchange membrane was assumed to influence the bipolar membrane selectivity.

Characterization of antibacterial polyethersulfone membranes using the Respiration Activity Monitoring System (RAMOS).

Membranes with antibacterial properties were developed using surface modification of polyethersulfone ultrafiltration membranes. Three different modification strategies using polyelectrolyte layer-by-layer (LbL) technique are described. The first strategy relying on the intrinsic antibacterial properties of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(ethylenimine) (PEI) exhibits only little antibacterial effects. The other two strategies contain silver in both ionic (Ag(+)) and metallic (Ag(0)) form. Ag(+) embedded into negatively charged poly(sodium 4-styrene sulfonate) (PSS) layers totally inhibits bacterial growth. Ag(0) nanoparticles were introduced to the membrane surface by LbL deposition of chitosan- and poly(methacrylic acid) - sodium salt (PMA)-capped silver nanoparticles and subsequent UV or heat treatment. Antibacterial properties of the modified membranes were quantified by a new method based on the Respiration Activity Monitoring System (RAMOS), whereby the oxygen transfer rates (OTR) of E. coli K12 cultures on the membranes were monitored online. As opposed to colony forming counting method RAMOS yields more quantitative and reliable data on the antibacterial effect of membrane modification. Ag-imprinted polyelectrolyte film composed of chitosan (Ag(0))/PMA(Ag(0))/chitosan(Ag(0)) was found to be the most promising among the tested membranes. Further investigation revealed that the concentration and equal distribution of silver in the membrane surface plays an important role in bacterial growth inhibition.

Fluorescent magnetoliposomes as a platform technology for functional and molecular MR and optical imaging

Here, we present a detailed characterisation of rhodamine B-containing magnetoliposomes (FLU-ML), emphasising the dependence of their fluorescence properties on the presence of iron oxide cores, and the molar fraction of the fluorophore. The magnetoliposome types used exist as colloidally stable, negatively charged clusters with an average hydrodynamic diameter of 95 nm. The molar rhodamine B fractions were 0.67 % and 1.97 %. Rhodamine B normalised fluorescence, quantum yields and fluorescence lifetimes were substantially reduced by inner filter effects as the magnetoliposome concentration is increased, by increasing molar rhodamine B fraction, and by quenching originating from the iron oxide cores. MR relaxometry at 3 T revealed extremely high r2 relaxivities (440 to 554 s-1mM-1) and moderately high r1 values (2.06 to 3.59 s-1mM-1). Upon incubating human prostate carcinoma (PC-3) cells with FLU-ML, a dose-dependent particle internalisation was found by MR relaxometry. In addition, the internalised FLU-ML were clearly visible by fluorescence microscopy. At the FLU-ML concentrations used (up to 3 × 10³ M Fe) cell viability was not substantially impaired. These results provide valuable insights on the fluorescence properties of bimodal magnetoliposomes and open promising perspectives for the use of these materials as a platform technology for advanced functional and molecular MR and optical imaging applications.

Characterization and filtration performance of coating-modified polymeric membranes used in membrane bioreactors

One of the critical issues for membrane application in wastewater treatment is membrane fouling majorly caused by dissolved organic matters. The aim of the present study was to lower membrane fouling by adsorption of polyelectrolytes. In the paper, the feasibility of coating for diverse ultrafiltration membrane materials was investigated and their filtration performance was compared to that of the unmodified ones. Different ultrafiltration flat-sheet membranes, polyvinylidene fluoride, polyethersulfone, polysulfone and cellulose acetate were coated by branched poly(ethyleneimine) (PEI), poly(diallyldimethylammonium chloride) (PDADMAC) and poly(allylamine chloride) (PAH) and filtrated with sludge supernatant. Short term experiments showed a substantial drop of permeability: almost 40 % for PEI, 23 % for PDADMAC, and about 19 % for PAH coating. This deterioration resulted from the additional resistance of the deposited layers. On the other hand, coating led to lower fouling rates during filtration. In the stable state of filtration, coated membranes showed higher permeabilities compared to the uncoated ones. For the polyethersulfone membrane, the average permeability enhancement was 11 %. For polysulfone and cellulose acetate membranes, the permeability improved by 28 % and 15 % respectively. For polyvinylidene fluoride membranes only coating with PDADMAC enhanced the permeability, by 13 %. PEI and PAH modified membranes featured lower permeabilities than the uncoated ones.