Layer-by-layer formation of oligoelectrolyte multilayers: a combined experimental and computational study

For the first time, the combination of experimental preparation and results of fully atomistic simulations of an oligoelectrolyte multilayer (OEM) made of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) (PDADMAC/PSS) is presented. The layer-by-layer growth was carried out by dipping silica substrates in oligoelectrolyte solutions and was modeled by means of atomistic molecular dynamics simulations with a protocol that mimics the experimental procedure up to the assembly of four layers. Measurements of OEM thickness, surface roughness and amount of adsorbed oligoelectrolyte chains obtained from both approaches are compared. A good agreement between simulated and experimental results was found, with some deviations due to intrinsic limitations of both methods. However, the combination of information extracted from simulations to support the analysis of experimental data can overcome such restrictions and improve the interpretation of experimental results. On the other hand, processes dominated by slower kinetics, like the destabilization of adsorbed layers upon equilibration with the surrounding environment, are out of reach for the simulation modeling approach, but they can be investigated by monitoring in situ the oligoelectrolyte adsorption during the assembly process. This demonstrates how the synergistic use of simulation and experiments improves the knowledge of OEM properties down to the molecular scale

One-step RAFT synthesis of well-defined amphiphilic star polymers and their self-assembly in aqueous solution

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Multifunctional chain transfer agents for RAFT polymerisation were designed for the one-step synthesis of amphiphilic star polymers. Thus, hydrophobically end-capped 3- and 4-arm star polymers, as well as linear ones for reference, were made of the hydrophilic monomer N,N-dimethylacrylamide (DMA) in high yield with molar masses up to 150 000 g mol−1, narrow molar mass distribution (PDI ≤ 1.2) and high end group functionality (∼90%). The associative telechelic polymers form transient networks of interconnected aggregates in aqueous solution, thus acting as efficient viscosity enhancers and rheology modifiers, eventually forming hydrogels. The combination of dynamic light scattering (DLS), small angle neutron scattering (SANS) and rheology experiments revealed that several molecular parameters control the structure and therefore the physical properties of the aggregates. In addition to the size of the hydrophilic block (maximum length for connection) and the length of the hydrophobic alkyl chain ends (stickiness), the number of arms (functionality) proved to be a key parameter.EC/FP7/226507/EU/Integrated Infrastructure Initiative for Neutron Scattering and Muon Spectroscopy/NMI

Structure-related differences in the temperature-regulated fluorescence response of LCST type polymers

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.BMBF, 03IS2201B, Spitzenforschung und Innovation in den Neuen Ländern - Das Taschentuchlabor: Impulszentrum für Integrierte Bioanalyse (IZIB

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Chem. Phys. 140, 034902 (2014) and may be found at https://doi.org/10.1063/1.4861894.The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence on the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.BMBF, 05K10KT1, Verbundprojekt NanoSOFT: Teilprojekt 2: Neutronen Spin-Echo Experimente zur Untersuchung komplexer Soft-Matter Systeme mit extremer Präzissio

Effect of Poly(Oxanorbonene)- and Poly(Methacrylate)-Based Polyzwitterionic Surface Coatings on Cell Adhesion and Gene Expression of Human Keratinocytes

Polyzwitterions are generally known for their anti-adhesive properties, including resistance to protein and cell adhesion, and overall high bio-inertness. Yet there are a few polyzwitterions to which mammalian cells do adhere. To understand the structural features of this behavior, a panel of polyzwitterions with different functional groups and overall degrees of hydrophobicity is analyzed here, and their physical and biological properties are correlated to these structural differences. Cell adhesion is focused on, which is the basic requirement for cell viability, proliferation, and growth. With the here presented polyzwitterion panel, three different types of cell-surface interactions are observed: adhesion, slight attachment, and cell repellency. Using immunofluorescence methods, it is found that human keratinocytes (HaCaT) form focal adhesions on the cell-adhesive polyzwitterions, but not on the sample that has only slight cell attachment. Gene expression analysis indicates that HaCaT cells cultivated in the presence of a non-adhesive polyzwitterion have up-regulated inflammatory and apoptosis-related cell signaling pathways, while the gene expression of HaCaT cells grown on a cell-adhesive polyzwitterion does not differ from the gene expression of the growth control, and thus can be defined as fully cell-compatible

Influence of the surfactant degree of oligomerization on the formation of cyclodextrin: surfactant inclusion complexes

Supramolecular complexation is an attractive strategy to modulate the performance of surfactants, e.g., by host-guest interactions. Here, we investigate the interaction of single-chained, di-, tri-, and tetrameric cationic surfactants with cyclodextrins by conductivity and 1H NMR measurements, exploring the effect of increasing the number of the surfactant hydrophobic tails on the stability of cyclodextrin:surfactant inclusion complexes. The stoichiometry and the binding equilibrium constants of the different inclusion complexes were elucidated. Under the working conditions, the number of hydrophobic chains was found not to affect stoichiometry and 1:1 inclusion complexes were formed for all the surfactants investigated. The stability of the host-guest complexes decreases from single-chained to dimeric (“gemini”) surfactants, the binding following a non-cooperative mechanism. This result may be rationalized by taking into account steric constraints and electrostatic effects as well as the need to overcome the hydrophobic interactions between the chains of the same surfactant molecule. However, a further increase in the number of hydrophobic tails, from two to three to four, results in an increase in the equilibrium binding constant, K1. In this case, an increment in the number of chains capable of interaction with the cyclodextrin molecules seems to be the main factor responsible for the increase in K1. ROESY spectra show the coexistence of different types of 1:1 host-guest complexes for tri- and tetrameric surfactants.Consejería de Innovación, Ciencia y Empresa de la Junta de Andalucía P12-FQM- 1105, FQM-274 y FQM-206University of Seville 2017/1004FEDER fund

Structures and Synthesis of Zwitterionic Polymers

The structures and synthesis of polyzwitterions (“polybetaines”) are reviewed, emphasizing the literature of the past decade. Particular attention is given to the general challenges faced, and to successful strategies to obtain polymers with a true balance of permanent cationic and anionic groups, thus resulting in an overall zero charge. Also, the progress due to applying new methodologies from general polymer synthesis, such as controlled polymerization methods or the use of “click” chemical reactions is presented. Furthermore, the emerging topic of responsive (“smart”) polyzwitterions is addressed. The considerations and critical discussions are illustrated by typical examples

Novel nonionic polymerisable surfactants based on sulfoxides. 1. Monomer synthesis and general surfactant behaviour

The synthesis, surface activity, and micellisation of a series of new nonionic polymerisable surfactants, often referred to as surfmers. are described. These monomers bear terminal vinyl groups or acrylic esters. and the nonionic sulfoxide moiety. Compared to many other nonionic hydrophilic fragments. the sulfoxide group behaves as a strongly hydrophilic fragment of small volume, that can balance up to an acryloyloxyundecyl hydrophobic chain. The incorporation of the polar acrylate moiety at the end of the hydrophobic chain seems to confer surfactant properties similar to the ones of bola amphiphiles to the monomers