Search Results (6)

Polymer-based membranes represent an irreplaceable group of materials that can be applied in a wide range of key industrial areas, from packaging to high-end technologies. Increased selectivity to transport properties or the possibility of controlling membrane permeability by external stimuli represents a key issue in current material research. In this work, we present an unconventional approach with the introduction of silver nanoparticles (AgNPs) into membrane pores, by immobilising them onto the surface of polyethyleneterephthalate (PET) foil with subsequent physical modification by means of laser and plasma radiation prior to membrane preparation. Our results showed that the surface characteristics of AgNP-decorated PET (surface morphology, AgNP content, and depth profile) affected the distribution and concentration of AgNPs in subsequent ion-track membranes. We believe that the presented approach affecting the redistribution of AgNPs in the polymer volume may open up new possibilities for the preparation of metal nanoparticle-filled polymeric membranes. The presence of AgNPs on the pore walls can facilitate the grafting of stimuli-responsive molecules onto these active sites and may contribute to the development of intelligent membranes with controllable transport properties. Full article

We performed molecular dynamics simulations to characterize the role of enthalpic interaction in impacting the static and dynamic properties of solvent-free polymer brushes. The intrinsic enthalpic interaction in the simulation was introduced using different attraction strengths between distinct species. Two model systems were considered: one consisting of binary brushes of two different polymer types and the other containing a mixture of homopolymer brushes and free molecules. In the first system, we observed that, when two originally incompatible polymers were grafted to opposing surfaces, the miscibility between them was significantly enhanced. A less favorable intrinsic enthalpic interaction in the brushes resulted in a more stretched chain configuration, a lower degree of inter-brush penetration, and faster segmental relaxation. In the second system, we characterized the solvent capacity of the homopolymer brushes from variations in the energy components of the system as a function of the number of free molecules. We determined that molecular absorption was driven by the release of the entropic frustration for the grafted chains in conjunction with the chemical affinity between the solutes and polymers. The solute distribution function within the inter-wall space showed that solute–polymer mixing in the middle of the gap occurred preferentially when the enthalpic interaction was more favorable. When this was not the case, absorption was predominantly localized near the grafting surface. From the mean square displacement of the solute, we found that the brush profiles restrained the molecular diffusion perpendicular to the grafting wall; the weaker the attraction from the brush, the higher the solute mobility. Full article

Zwitterionic polymers as crucial antifouling materials exhibit excellent antifouling performance due to their strong hydration ability. The structure–property relationship at the molecular level still remains to be elucidated. In this work, the surface hydration ability of three antifouling polymer membranes grafting on polysiloxane membranes Poly(sulfobetaine methacrylate) (T4-SB), poly(3-(methacryloyloxy)propane-1-sulfonate) (T4-SP), and poly(2-(dimethylamino)ethyl methacrylate) (T4-DM) was investigated. An orderly packed, and tightly bound surface hydration layer above T4-SP and T4-SB antifouling membranes was found by means of analyzing the dipole orientation distribution, diffusion coefficient, and average residence time. To further understand the surface hydration ability of three antifouling membranes, the surface structure, density profile, roughness, and area percentage of hydrophilic surface combining electrostatic potential, RDFs, SDFs, and noncovalent interactions of three polymers’ monomers were studied. It was concluded that the broadest distribution of electrostatic potential on the surface and the nature of anionic SO3- groups led to the following antifouling order of T4-SB > T4-SP > T4-DM. We hope that this work will gain some insight for the rational design and optimization of ecofriendly antifouling materials. Full article

Structural and morphological features of graft polystyrene (PS) and polyethylene (PE) copolymers produced by post-radiation chemical polymerization have been investigated by methods of X-ray microanalysis, electron microscopy, DSC and wetting angles measurement. The studied samples differed in the degree of graft, iron(II) sulphate content, sizes of PE films and distribution of graft polymer over the polyolefin cross section. It is shown that in all cases sample surfaces are enriched with PS. As the content of graft PS increases, its concentration increases both in the volume and on the surface of the samples. The distinctive feature of the post-radiation graft polymerization is the stepped curves of graft polymer distribution along the matrix cross section. A probable reason for such evolution of the distribution profiles is related to both the distribution of peroxide groups throughout the sample thickness and to the change in the monomer and iron(II) salt diffusion coefficients in the graft polyolefin layer. According to the results of electron microscope investigations and copolymer wettability during graft polymerization, a heterogeneous system is formed both in the sample volume and in the surface layer. It is shown that the melting point, glass transition temperature and degree of crystallinity of the copolymer decreases with the increasing proportion of graft PS. It is suggested that during graft polymerization a process of PE crystallite decomposition (melting) and enrichment of the amorphous phase of graft polymer by fragments of PE macromolecules occurs spontaneously. The driving force of this process is the osmotic pressure exerted by the phase network of crystallites on the growing phase of the graft PS. Full article

Cytotoxic agents that are used conventionally in cancer therapy present limitations that affect their efficacy and safety profile, leading to serious adverse effects. In the aim to overcome these drawbacks, different approaches have been investigated and, among them, theranostics is attracting interest. This new field of medicine combines diagnosis with targeted therapy; therefore, the aim of this study was the preparation and characterization of Molecularly Imprinted Polymers (MIPs) selective for the anticancer drug Sunitinib (SUT) for the development of a novel theranostic system that is able to integrate the drug controlled release ability of MIPs with Rhodamine 6G as a fluorescent marker. MIPs were synthesized by precipitation polymerization and then functionalized with Rhodamine 6G by radical grafting. The obtained polymeric particles were characterized in terms of particles size and distribution, ξ-potential and fluorescent, and hydrophilic properties. Moreover, adsorption isotherms and kinetics and in vitro release properties were also investigated. The obtained binding data confirmed the selective recognition properties of MIP, revealing that SUT adsorption better fitted the Langmuir model, while the adsorption process followed the pseudo-first order kinetic model. Finally, the in vitro release studies highlighted the SUT controlled release behavior of MIP, which was well fitted with the Ritger-Peppas kinetic model. Therefore, the synthesized fluorescent MIP represents a promising material for the development of a theranostic platform for Sunitinib controlled release and self-monitoring in cancer therapy. Full article

Polymer brushes are outstanding lubricants that can strongly reduce wear and friction between surfaces in sliding motion. In recent decades, many researchers have put great effort in obtaining a clear understanding of the origin of the lubricating performance of these brushes. In particular, molecular dynamics simulations have been a key technique in this scientific journey. They have given us a microscopic interpretation of the tribo-mechanical response of brushes and have led to the prediction of their shear-thinning behavior, which has been shown to agree with experimental observations. However, most studies so far have focused on parallel plate geometries, while the brush-covered surfaces might be highly curved in many applications. Here, we present molecular dynamics simulations that are set up to study the friction for brushes grafted on the exterior of cylinders that are moving inside larger cylinders that bear brushes on their interior. Our simulations show that the density distributions for brushes on the interior or exterior of these cylinders are qualitatively different from the density profiles of brushes on flat surfaces. In agreement with theoretical predictions, we find that brushes on the exterior of cylinders display a more gradual decay, while brushes on the interior of cylinders becomes denser compared to flat substrates. When motion is imposed, the density profiles for cylinder-grafted brushes adapt qualitatively differently to the shear motion than observed for the parallel plate geometry: the zone where brushes overlap moves away from its equilibrium position. Surprisingly, and despite all these differences, we observe that the effective viscosity is independent of the radius of the brush-grafted cylinders. The reason for this is that the viscosity is determined by the overlap between the brushes, which turns out to be insensitive to the exact density profiles. Our results provide a microscopic interpretation of the friction mechanism for polymer brushes in cylindrical geometries and will aid the design of effective lubricants for these systems. Full article