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

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

Implementation of a Hardware/Software Platform for Real-Timedata-Intensive Applications in Hazardous Environments

Real-Time Technology and Applications Symposium. Brookline, MA, USA, 10-12 Oct. 1996In real-time data-intensive applications, the simultaneous achievement of the required performance and determinism is a difficult issue to address, mainly due to the time needed to perform I/O operations, which is more significant than the CPU processing time. Additional features need to be considered if these applications are intended to perform in hostile environments. In this paper, we address the implementation of a hardware/software platform designed to acquire, transfer, process and store massive amounts of information at sustained rates of several MBytes/sec, capable of supporting real-time applications with stringent throughput requirements under hazardous environmental conditions. A real-world system devoted to the inspection of nuclear power plants is presented as an illustrative examplePublicad

Coherent caloritronics in Josephson-based nanocircuits

We describe here the first experimental realization of a heat interferometer, thermal counterpart of the well-known superconducting quantum interference device (SQUID). These findings demonstrate, on the first place, the existence of phase-dependent heat transport in Josephson-based superconducting circuits and, on the second place, open the way to novel ways of mastering heat at the nanoscale. Combining the use of external magnetic fields for phase biasing and different Josephson junction architectures we show here that a number of heat interference patterns can be obtained. The experimental realization of these architectures, besides being relevant from a fundamental physics point of view, might find important technological application as building blocks of phase-coherent quantum thermal circuits. In particular, the performance of two different heat rectifying devices is analyzed.Comment: 34 pages, 15 figures, review article for Ultra-low temperatures and nanophysics ULTN2013. Microkelvin Proceeding