Sediment traps with guiding channel and hybrid check dams improve controlled sediment retention

Sediment traps with partially open check dams are crucial elements for flood protection in alpine regions. The trapping of sediment is necessary when intense sediment transport occurs during floods that may endanger urban areas at downstream river reaches. In turn, the unwanted permanent trapping of sediment during small, non-hazardous floods can result in the ecological and morphological degradation of downstream reaches. This study experimentally analyses a novel concept for permeable sediment traps. For ensuring the sediment transfer up to small floods, a guiding channel implemented in the deposition area of a sediment trap was systematically studied. The bankfull discharge of the guiding channel corresponds to a dominant morphological discharge. At the downstream end of the guiding channel, a permeable barrier (check dam) triggers sediment retention and deposition. The permeable barrier consists of a bar screen for mechanical deposition control, superposed to a flow constriction for the hydraulic control. The barrier obstructs hazardous sediment transport for discharges that are higher than the bankfull discharge of the guiding channel without the risk of unwanted sediment flushing (massive selfcleaning)

A Fluorescent Thermometer Based on a Pyrene-Labeled Thermoresponsive Polymer

Thermoresponsive polymers that undergo a solubility transition by variation of the temperature are important materials for the development of ‘smart’ materials. In this contribution we exploit the solubility phase transition of poly(methoxy diethylene glycol methacrylate), which is accompanied by a transition from hydrophilic to hydrophobic, for the development of a fluorescent thermometer. To translate the polymer phase transition into a fluorescent response, the polymer was functionalized with pyrene resulting in a change of the emission based on the microenvironment. This approach led to a soluble polymeric fluorescent thermometer with a temperature range from 11 °C to 21 °C. The polymer phase transition that occurs during sensing is studied in detail by dynamic light scattering

Thin Polymer Brush Decouples Biomaterial's Micro-/Nano-Topology and Stem Cell Adhesion

Surface morphology and chemistry of polymers used as biomaterials, such as tissue engineering scaffolds, have a strong influence on the adhesion and behavior of human mesenchymal stem cells. Here we studied semicrystalline poly(ε-caprolactone) (PCL) substrate scaffolds, which exhibited a variation of surface morphologies and roughness originating from different spherulitic superstructures. Different substrates were obtained by varying the parameters of the thermal processing, i.e. crystallization conditions. The cells attached to these polymer substrates adopted different morphologies responding to variations in spherulite density and size. In order to decouple substrate topology effects on the cells, sub-100 nm bio-adhesive polymer brush coatings of oligo(ethylene glycol) methacrylates were grafted from PCL and functionalized with fibronectin. On surfaces featuring different surface textures, dense and sub-100 nm thick brush coatings determined the response of cells, irrespective to the underlying topology. Thus, polymer brushes decouple substrate micro-/nano-topology and the adhesion of stem cells

One step ATRP initiator immobilization on surfaces leading to gradient-grafted polymer brushes

Published: April 30, 2014A method is described that allows potentially any surface to be functionalized covalently with atom transfer radical polymerization (ATRP) initiators derived from ethyl-2-bromoisobutyrl bromide in a single step. In addition, the initiator surface density was variable and tunable such that the thickness of polymer chain grafted from the surface varied greatly on the surfaces providing examples, across the surface of a substrate, of increased chain stretching due to the entropic nature of crowded polymer chains leading toward polymer brushes. An initiator gradient of increasing surface density was deposited by plasma copolymerization of an ATRP initiator (ethyl 2-bromoisobutyrate) and a non-ATRP reactive diluent molecule (ethanol). The deposited plasma polymer retained its chemical ability to surface-initiate polymerization reactions as exemplified by N,N'-dimethyl acrylamide and poly(ethylene glycol) methyl ether methacrylate polymerizations, illustrating linear and bottle-brush-like chains, respectively. A large variation in graft thickness was observed from the low to high chain-density side suggesting that chains were forced to stretch away from the surface interface--a consequence of entropic effects resulting from increased surface crowding. The tert-butyl bromide group of ethyl 2-bromoisobutyrate is a commonly used initiator in ATRP, so a method for covalent linkage to any substrate in a single step desirably simplifies the multistep surface activation procedures currently used.Bryan R. Coad, Katie E. Styan, and Laurence Meaghe

Functional polymer brushes via surface-initiated controlled radical polymerizations

The term polymer brush refers to a well defined arrangement of polymer chains, which are tethered with one end to an interface and usually the surface of a solid substrate. Due to steric repulsion the polymer chains furthermore adopt a defined, stretched chain conformation, which significantly differs from the random walk conformation of free polymer chains in solution or in conventionally solution casted polymer coatings. From a structural point of view polymer brushes can therefore be regarded as the most defined type of polymer coating that can currently be realized. Especially the combination of surface-initiated polymerizations (SIP) with modern, controlled polymerization methods thereby allows tailoring the structure of the polymer brushes almost on the molecular level. Specifically precise control over the thickness, composition, chain architecture, grafting density and via the use of lithographic techniques also over the topography of the brushes can be achieved. This high degree of control over the structural and implicated (physico-)chemical properties of the brush allows at the same time tailoring and fine tuning the interfacial properties of the brush. This thesis describes the systematic exploitation of well-defined polymer brushes as functional coatings with fine-tuned physicochemical properties to direct and control the interaction with and the response of specific biological, bioanalytical and even reactive chemical environments. In detail the use of surface-initiated atom transfer radical polymerization (SI-ATRP) for the fabrication of functional polymer brushes will be presented. These brushes were used as highly defined coatings in various applications ranging from biomedical and bioanalytical applications to biomimetic materials fabrication (Figure 1). Figure 1 Numerous synthetic approaches for the preparation of polymer brushes have been described in the literature. Chapter 2 will therefore present a summary of the most important types of surface-initiated polymerizations, focusing especially on controlled SIP methods and SI-ATRP. Chapter 3 describes a chemoselective and specific immobilization strategy to decorate intrinsically bioinert polymer brushes with proteins of interest in a defined orientation and density. Specifically the resulting substrates represent attractive candidates for the realization of protein microarrays. In view of this application protein-small molecule and protein-protein interactions as well as posttranslational modifications were analyzed within a feasibility study. Due to their well-defined structure polymer brushes represent also attractive candidates for the realization of molecularly defined cell adhesion substrates for tissue engineering or as highly defined biophysical model system to analyze cell adhesion and mechanics. Chapter 4 describes the decoration of intrinsically bioinert polymer brushes with small peptide ligands with defined density to induce integrin specific cell adhesion on the brushes. Peptide functionalized polymer brushes could be readily endothelialized and adhering cell layers have shown to preserve their homeostatic ability to respond to an applied mechanical stimulus in a physiological manner. In Chapter 5 the limitations of high density polymer brushes in biomedical applications were assessed by analyzing their stability under in vitro cell culture conditions. Intrinsically bioinert high density polymer brushes were found to degraft from glass or silicon substrates upon swelling in good solvents, which lead to deterioration of the bioinert properties of the substrate. The degrafting of the brushes might be connected to swelling induced mechanical activation of chemical bonds, which link the brushes to the substrate. Chapter 6 describes the transfer of the developed SIP approach onto flexible PDMS substrates by exploiting the formation of interpenetrating networks of ATRP-initiator siloxane and PDMS. The modification of the PDMS substrates with hydrophilic brushes effectively reduces the unspecific protein adsorption on the substrates. This approach might therefore represent an attractive and facile route for the surface modification of miniaturized PDMS devices for biomedical or bioanalytical applications. In Chapter 7 the systematic development of a reliable and robust protocol for the aqueous SI-ATRP of sodium methacrylate is presented, which gives access to poly(methacrylic acid) (PMAA) brushes with defined molecular weight and grafting density. The resulting brushes were assessed for their ability to direct the mineralization of calcium carbonate. Chapter 8 describes the use of photolithographically patterned poly(methacrylic acid) brushes as biomimetic, acidic macromolecular matrix to fabricate microstructured calcite thin films that are an exact 3D replica of the PMAA brush. The presented strategy relies on three key elements: (i) the use of photolithographic techniques to prepare microstructured PMAA brushes; (ii) the ability of PMAA brushes to stabilize amorphous calcium carbonate (ACC) and (iii) the possibility to convert the metastable ACC phase into a polycrystalline calcite film via a thermal treatment

Vortici quantizzati nei superfluidi bosonici tramite l'equazione di Gross-Pitaevskii

Abbiamo trattato diverse proprietà dei vortici quantizzati nei superfluidi bosonici. Partendo dalle equazioni di Hartree e di Gross-Pitaevskii stazionaria (GPE), abbiamo sottolineato come esse siano adatte a descrivere sistemi quali i gas diluiti ultrafreddi. Poi si è passati allo studio della forma dei vortici quantizzati sia in assenza di potenziale esterno sia in presenza di un potenziale armonico: per quest'ultimo problema abbiamo proposto due approssimazioni delle soluzioni della GPE

Surface Modification of Polydimethylsiloxane Substrates with Nonfouling Poly(Poly(ethylene glycol)methacrylate) Brushes

This contribution presents a new strategy to grow nonfouling poly (poly(ethylene glycol) methacrylate) (PPEGMA) brushes from polydimethylsiloxane (PDMS) substrates. The strategy presented here is based on the use of a sequence of vapor deposition/hydrolysis cycles to generate a surface-confined atom transfer radical polymerization (ATRP)-initiator functionalized interpenetrating polymer network (IPN) layer. In contrast to most other approaches that have been developed to graft thin polymer layers from PDMS substrates, this technique obviates the need for UV/ozone pretreatment of the PDMS substrate. it is shown that the surface-confined ATRP-initiator functionalized IPN layer can be used to grow PPEGMA brushes in a controlled fashion and that the resulting PPEGMA coating significantly reduces nonspecific protein adsorption as compared to unmodified PDMS substrates