Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

SEM and EDS Characterisation of Layering TiOx Growth onto the Cutting Tool Surface in Hard Drilling Processes of Ti-Al-V Alloys

10 p.

Proof of Concept of Impact Detection in Composites Using Fiber Bragg Grating Arrays

Impact detection in aeronautical structures allows predicting their future reliability and performance. An impact can produce microscopic fissures that could evolve into fractures or even the total collapse of the structure, so it is important to know the location and severity of each impact. For this purpose, optical fibers with Bragg gratings are used to analyze each impact and the vibrations generated by them. In this paper it is proven that optical fibers with Bragg gratings can be used to detect impacts, and also that a high-frequency interrogator is necessary to collect valuable information about the impacts. The use of two interrogators constitutes the main novelty of this paper.

Advances in Click Chemistry for Single-Chain Nanoparticle Construction

Single-chain polymeric nanoparticles are artificial folded soft nano-objects of ultra-small size which have recently gained prominence in nanoscience and nanotechnology due to their exceptional and sometimes unique properties. This review focuses on the current state of the investigations of click chemistry techniques for highly-efficient single-chain nanoparticle construction. Additionally, recent progress achieved for the use of well-defined single-chain nanoparticles in some promising fields, such as nanomedicine and catalysis, is highlighted.

Metal-Free Polymethyl Methacrylate (PMMA) Nanoparticles by Enamine "Click" Chemistry at Room Temperature

"Click" chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the "metal-free" cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing beta-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of beta-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine "click" chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs.

Global movements, national grievances. Mobilizing for “real democracy” and social justice

In the ashes of political and socio-economic collapse, social movements sometimes rise like a phoenix. Little more than a year has passed since the Tunisian uprisings, the spark that ignited a series of “mobilizations of the indignant” that spread like wildfire around the world. Many observers have reported on these unprecedented global protests. They have portrayed citizens who declare feeling marginalized if not scapegoated, and who reject the increasing inequalities between rich and poor, the declining mobility of most, and the “disclassment” of many. They have shown, as well, massive protests against governments and politicians that are perceived as indifferent at best, duplicitous at worst, and in any event as blatantly closed to popular concerns. Many journalists have indeed asked what took so long for people to protest given this fatal combination. For the social scientist, however, the questions of who, why and how mobilizes are not so simple. There are specific problematics of mediation between structure, culture and individual or collective agency that need to be addressed.

Eurasian integration as a way to respond to global challenges

510 p.

Plastic Analysis and Testing of multidirectional SFRC flag slabs

This paper presents a theoretical and experimental study of multidirectional steel fibers reinforced concrete slabs (SFRC). The study is based on a real building application using SFRC flag slabs. For the evaluation of the slabs bearing capacity, plastic calculations are performed both at section and structure levels. The section analysis uses the perfect plastic stress-strain diagram, with reference to the values of the strength characteristics of SFRC based on previous jobs that used similar fibers and dosages. In the structure analysis the plastic yield lines method has been used. This method relates the section last bearing moment and the plastic collapse load. The experimental campaign has consisted of the testing of six 2 m. diameter circular shaped slabs prototypes, and has allowed to verify the reference resistance used in the calculations.

La crisis actual: una visión desde la transparencia y las medidas al respecto

[ES]Este trabajo tiene como objetivo fundamental, valorar si podría haber sido distinto el transcurso de la crisis actual de haber existido mayor transparencia. Al mismo tiempo, también se tratan de observar tanto las medidas actuales como futuras tomadas al respecto. Para ello, se plantean una serie de objetivos secundarios con la finalidad de conseguir de esta manera guiar el desarrollo ordenado de los acontecimientos. Uno de estos objetivos es ver cuál ha sido el origen y desarrollo de la crisis. Para ello, se ha planteado el surgimiento de las hipotecas subprime, base de un sistema que empezó a fallar cuando muchas de estas fueron insolventes. Además, la globalización del sistema financiero contribuyó a que el número de afectados por la titulización de estas hipotecas, un procedimiento muy habitual entonces, fuese mayor. De esta manera, la crisis que surgió originariamente en Estados Unidos pasó a afectar prácticamente a todos los demás países. Otros de los objetivos, están centrados alrededor de la falta de transparencia, sus consecuencias y las medidas paliativas tomadas tanto presentes como futuras. Todo esto se ha planteado acerca de varios aspectos, pero quizás los más importante son los que tratan acerca de la transparencia de los procedimientos bancarios, los cuales debido a su opacidad contribuyeron a generar desconfianza en el sistema interbancario, derivando en un colapso del mismo y en crisis de liquidez.

Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

Single-chain technology (SCT) allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs) via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful "click" chemistry driving force for SCNP construction. By employing poly(methyl methacrylate)- (PMMA-) based copolymers bearing beta-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC), infrared (IR) spectroscopy, proton nuclear magnetic resonance (H-1 NMR) spectroscopy, dynamic light scattering (DLS), and elemental analysis (EA).