Role of radicals in UV‐initiated postplasma grafting of poly‐ε‐caprolactone: An electron paramagnetic resonance study

Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The blogosphere as an excitable social medium: Richter’s and Omori’s Law in media coverage

We study the dynamics of public media attention by monitoring the content of online blogs. Social and media events can be traced by the propagation of word frequencies of related keywords. Media events are classified as exogenous–where blogging activity is triggered by an external news item–or endogenous where word frequencies build up within a blogging community without external influences. We show that word occurrences exhibit statistical similarities to earthquakes. Moreover the size distribution of events scales with a similar exponent as found in the Gutenberg–Richter law. The dynamics of media events before and after the main event can be satisfactorily modeled as a type of process which has been used to understand fore–and aftershock rate distributions in earthquakes–the Omori law. We present empirical evidence that for media events of endogenous origin the overall public reception of the event is correlated with the behavior of word frequencies at the beginning of the event, and is to a certain degree predictable. These results imply that the process of opinion formation in a human society might be related to effects known from excitable media.     

Reaction rate theory for supramolecular kinetics: application to protein aggregation

ABSTRACT

Probing reaction mechanisms of supramolecular processes in soft and biological matter, such as protein aggregation, is inherently challenging. This is because these processes involve multiple molecular mechanisms that are associated with the rearrangement of large numbers of weak bonds, resulting in complex free energy landscapes with many kinetic barriers. Reaction rate measurements at different temperatures can offer unprecedented insights into the underlying molecular mechanisms. However, to be able to interpret such measurements, a key challenge is to establish which properties of the complex free energy landscapes are probed by the reaction rate. Here, we present a reaction rate theory for supramolecular kinetics based on Kramers theory of diffusive reactions over multiple kinetic barriers. We find that reaction rates for protein aggregation are of the Arrhenius–Eyring type and that the associated activation energies probe only one relevant barrier along the respective free energy landscapes. We apply this advancement to interpret, in experiments and in coarse-grained computer simulations, reaction rates of amyloid aggregation in terms of molecular mechanisms and associated thermodynamic signatures. These results suggest a practical extension of the concept of rate-determining steps for complex supramolecular processes and establish a general platform for probing the underlying energy landscape using kinetic measurements.     

Experimental realization of maximum confidence quantum state discrimination for the extraction of quantum information

We present the first experimental demonstration of the maximum confidence measurement strategy for quantum state discrimination. Applying this strategy to an arbitrary set of states assigns to each input state a measurement outcome which, when realized, gives the highest possible confidence that the state was indeed present. The theoretically optimal measurement for discriminating between three equiprobable symmetric qubit states is implemented in a polarization-based free-space interferometer. The maximum confidence in the measurement result is 2/3. This is the first explicit demonstration that an improvement in the confidence over the optimal minimum error measurement is possible for linearly dependent states.