Synthesis, thermal behavior, and aggregation in aqueous solution of poly(methyl methacrylate)-b-poly(2-hydroxyethyl methacrylate)

Indexación: ScieloABSTRACT Amphiphilic block copolymers of poly(methyl methacrylate) PMMA and poly(2-hidroxyethyl methacrylate) PHEMA were synthesized by a two-step atom transfer radical polymerization (ATRP). Copolymers with various degrees of polymerization and different relative block sizes were obtained. The structure of the resulting polymers have been characterized and verified by FT-IR and 1H-NMR, molecular weight were determined by size exclusion chromatography analyses. The thermal properties of these polymers were investigated by differential scanning calorimetry DSC and thermogravimetric analysis TGA. The glass transition temperature of mono halogenated PMMA increases from 116 °C to 123 °C with increasing molecular weight, whereas the glass transition temperature of block copolymers depends slightly on polymer structure. The derivatives of TGA curves indicate that thermal degradation occurs in one stage. The self-assembly of PMMA-b-PHEMA in aqueous solution have been investigated by fluorescence probing methods. The critical micelle concentrations are in the range 10-6 - 10-7 M. The micropolarity sensed by pyrene is higher than in aggregates formed by block copolymers based on polystyrene. Keywords: Block copolymers, glass transition temperature, thermogravimetric analysis, critical micelle concentration, fluorescence probing methods

Can ultrastrong coupling change ground state chemical reactions?

Recent advancements on the fabrication of organic micro- and nanostructures have permitted the strong collective light-matter coupling regime to be reached with molecular materials. Pioneering works in this direction have shown the effects of this regime in the excited state reactivity of molecular systems and at the same time has opened up the question of whether it is possible to introduce any modifications in the electronic ground energy landscape which could affect chemical thermodynamics and/or kinetics. In this work, we use a model system of many molecules coupled to a surface-plasmon field to gain insight on the key parameters which govern the modifications of the ground-state Potential Energy Surface (PES). Our findings confirm that the energetic changes per molecule are determined by single-molecule-light couplings which are essentially local, in contrast with those of the electronically excited states, for which energetic corrections are of a collective nature. Still, we reveal some intriguing quantum-coherent effects associated with pathways of concerted reactions, where two or more molecules undergo reactions simultaneously, and which can be of relevance in low-barrier reactions. Finally, we also explore modifications to nonadiabatic dynamics and conclude that, for this particular model, the presence of a large number of dark states yields negligible changes. Our study reveals new possibilities as well as limitations for the emerging field of polariton chemistry

Ethnographic Experiments with Artists, Designers and Boundary Objects: Exhibitions as a research method

Ethnographic Experiments with Artists, Designers and Boundary Objects is a lively investigation into anthropological practice. Richly illustrated, it invites the reader to reflect on the skills of collaboration and experimentation in fieldwork and in gallery curation, thereby expanding our modes of knowledge production. At the heart of this study are the possibilities for transdisciplinary collaborations, the opportunity to use exhibitions as research devices, and the role of experimentation in the exhibition process. Francisco Martínez increases our understanding of the relationship between contemporary art, design and anthropology, imagining creative ways to engage with the contemporary world and developing research infrastructures across disciplines. He opens up a vast field of methodological explorations, providing a language to reconsider ethnography and objecthood while producing knowledge with people of different backgrounds

The Specification Property for C0C_0-Semigroups

We study one of the strongest versions of chaos for continuous dynamical systems, namely the specification property. We extend the definition of specification property for operators on a Banach space to strongly continuous one-parameter semigroups of operators, that is, $C_0$-semigroups. In addition, we study the relationships of the specification property for $C_0$-semigroups (SgSP) with other dynamical properties: mixing, Devaney's chaos, distributional chaos and frequent hypercyclicity. Concerning the applications, we provide several examples of semigroups which exhibit the SgSP with particular interest on solution semigroups to certain linear PDEs, which range from the hyperbolic heat equation to the Black-Scholes equation.Comment: 13 page

Efficient memory management in VOD disk array servers usingPer-Storage-Device buffering

We present a buffering technique that reduces video-on-demand server memory requirements in more than one order of magnitude. This technique, Per-Storage-Device Buffering (PSDB), is based on the allocation of a fixed number of buffers per storage device, as opposed to existing solutions based on per-stream buffering allocation. The combination of this technique with disk array servers is studied in detail, as well as the influence of Variable Bit Streams. We also present an interleaved data placement strategy, Constant Time Length Declustering, that results in optimal performance in the service of VBR streams. PSDB is evaluated by extensive simulation of a disk array server model that incorporates a simulation based admission test.This research was supported in part by the National R&D Program of Spain, Project Number TIC97-0438.Publicad