Andreas Fery

Elastic properties of polyelectrolyte capsules studied by atomic-force microscopy and RICM

Abstract.Mechanical properties of polyelectrolyte multilayer capsules were studied using a new method combining atomic-force microscopy and reflection interference contrast microscopy. By measuring the force vs. deformation for poly(styrene sulfonate)/poly(allylamine) capsules the existence of different deformation regimes depending on the applied deformation was shown. The present paper focuses on the small-deformation regime. The elastic response of the deformed capsule was studied as a function of the wall thickness and the capsule size, and showed the theoretically expected variations. The Young modulus obtained from the experiments ranges between 1.3 and 1.9 GPa.

Mechanics of artificial microcapsules

In recent years, an increasing number of microcapsule systems have been realized and have found applications in various fields of research and technology. Amongst others, polyelectrolyte multilayer capsules (PMCs) offer a great variety of materials and superior control over the wall thicknesses. We present here a review on the different techniques that are available for characterizing the mechanical properties of PMCs. We compare results that were obtained using these techniques on the same system, namely PMCs made from polyallylamine and polystyrenesulfonate multilayers and discuss perspectives of the field.

On the mechanical stability of polymeric microcontainers functionalized with nanoparticles

We present key factors that influence the mechanical stability of polyelectrolyte/nanoparticle composite microcontainers and their encapsulation behavior by thermal shrinkage. Poly(diallyldimethylammonium chloride) (PDADMAC), poly(styrenesulfonate) (PSS) microshells and citrate-stabilized gold nanoparticles are used. The presence of nanoparticles in the microshell renders the encapsulation process by heat-shrinking more difficult. The encapsulation efficiency is found to decrease as the concentration of material to be encapsulated increases. Increasing nanoparticle content in the microshell or the concentration of dextran increases the likelihood of getting fused and damaged capsules during encapsulation. On the other hand, mechanical studies show that doping microshells with gold nanoparticles significantly increases their stiffness and resistance to deformation. Internalization of capsules by cells supports that the incorporation of metal nanoparticles makes the shells more resistant to deformation. This work provides information of significant interest for the potential biomedical applications of polymeric microshells such as intracellular storage and delivery.

Organized Plasmonic Clusters with High Coordination Number and Extraordinary Enhancement in Surface- Enhanced Raman Scattering (SERS)**

Noble metal nanoparticles exhibit optical excitations known as surface plasmons that produce large enhancement of the local light intensity under external illumination, particularly when the nanoparticles are arranged in closely spaced configurations.1 The interparticle gap distance2 plays a critical role in the generation of hotspots with high electromagnetic fields, and thus such assembled nanoparticles find application to ultrasensitive detection, for example through surface-enhanced Raman scattering3 (SERS) and nonlinear optics, among other feats.4 Controlled assembly using colloidal chemistry is an emerging and promising field for high-yield production of metal nanoparticle clusters with small interparticle gaps.5 However, most of the reported methods rely on the use of nucleic acids or other organic molecules as linking elements,6 which yield long separation distances and thus weak plasmon coupling. Additionally, only simple clusters, such as dimers and trimers, have been efficiently synthesized. Herein, we report the controlled assembly of gold nanospheres into well-defined nanoparticle clusters with large coordination numbers (up to 7) and high symmetry. We further demonstrate ultrasensitive direct and indirect SERS sensing, thus corroborating the outstanding optical performance of these clusters with robust enhancement factors that are over three orders of magnitude higher than those of single particles.

Physical chemistry of encapsulation and release

This review describes recently introduced methods of coating colloidal particles and fabrication of hollow multilayer polyelectrolyte capsules. Diffusion through multilayer, Donnan equilibria for ions inside and outside hollow spheres and mechanical properties are given in quantitative aspects.

Stiffness-Dependent In Vitro Uptake and Lysosomal Acidification of Colloidal Particles

The physico-chemical properties of colloidal particles determine their uptake into cells. For a series of microparticles only one parameter, the mechanical stiffness, was varied, whereas other parameters such as size, shape, and charge were kept constant. The uptake was monitored in situ by analyzing individual particle trajectories including the progress of endocytosis, derived from local pH measurements around each particle. Evidence is presented that soft particles with low stiffness are transported faster to lysosomes than stiffer ones.

Cavitation Engineered 3D Sponge Networks and Their Application in Active Surface Construction

The design of the 3D architecture surfaces with both space- and time-dependent functionality (cell attraction, pH-trigged self-cleaning, antiseptic/disinfection) is in the focus. The innovative story includes: sonochemical surface activation, formation of feedback surface component (pH-responsible micelles), proof of responsive activity (time resolved cell adhesion and bacteria deactivation) and space adhesion selectivity (surface patterning).

Microcapsule mechanics : From stability to function

Microcapsules are reviewed with special emphasis on the relevance of controlled mechanical properties for functional aspects. At first, assembly strategies are presented that allow control over the decisive geometrical parameters, diameter and wall thickness, which both influence the capsules mechanical performance. As one of the most powerful approaches the layer-by-layer technique is identified. Subsequently, ensemble and, in particular, single-capsule deformation techniques are discussed. The latter generally provide more in-depth information and cover the complete range of applicable forces from smaller than pN to N. In a theory chapter, we illustrate the physics of capsule deformation. The main focus is on thin shell theory, which provides a useful approximation for many deformation scenarios. Finally, we give an overview of applications and future perspectives where the specific design of mechanical properties turns microcapsules into (multi-)functional devices, enriching especially life sciences and material sciences.

Strongly Coupled Plasmonic Modes on Macroscopic Areas via Template-Assisted Colloidal Self-Assembly

We present ensembles of surface-ordered nanoparticle arrangements, which are formed by template-assisted self-assembly of monodisperse, protein-coated gold nanoparticles in wrinkle templates. Centimeter-squared areas of highly regular, linear assemblies with tunable line width are fabricated and their extinction cross sections can be characterized by conventional UV/vis/NIR spectroscopy. Modeling based on electrodynamic simulations shows a clear signature of strong plasmonic coupling with an interparticle spacing of 1–2 nm. We find evidence for well-defined plasmonic modes of quasi-infinite chains, such as resonance splitting and multiple radiant modes. Beyond elementary simulations on the individual chain level, we introduce an advanced model, which considers the chain length distribution as well as disorder. The step toward macroscopic sample areas not only opens perspectives for a range of applications in sensing, plasmonic light harvesting, surface enhanced spectroscopy, and information technology but also eases the investigation of hybridization and metamaterial effects fundamentally.

Thermoresponsive PEG-based polymer layers: surface characterization with AFM force measurements.

Thermoresponsive polymer-coated surfaces based on poly(2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol) methacrylate) [P(MEO(2)MA-co-OEGMA)] allow switching between cell attachment and detachment. Here, we investigate the temperature-dependent surface interactions between the polymer coating and a colloidal probe in an aqueous medium by means of atomic force microscopy (AFM) force-distance measurements. The analysis of the adhesion forces from AFM retraction curves identifies two kinds of regimes for the copolymer at temperatures below and above the lower critical solution temperature (LCST). Whereas at 25 degrees C the surface interactions with the polymer in the swollen state are dominated by repulsive forces, at 37 degrees C the surface interactions switch to attractive forces and a stronger adhesion is detected by AFM. Running several heating/cooling cycles repeatedly shows that switching the surface properties provides reproducible adhesion force values. Time-dependent measurements give insight into the switching kinetics, demonstrating that the cell response is coupled to the polymer kinetics but probably limited by the cellular rearrangements.