Micro- vs. macro-phase separation in binary blends of poly(styrene)-poly(isoprene) and poly(isoprene)-poly(ethylene oxide) diblock copolymers

In this paper we present an experimentally determined phase diagram of binary blends of the diblock copolymers poly(styrene)-poly(isoprene) and poly(isoprene)-poly(ethylene oxide). At high temperatures, the blends form an isotropic mixture. Upon lowering the temperature, the blend macro-phase separates before micro-phase separation occurs. The observed phase diagram is compared to theoretical predictions based on experimental parameters. In the low-temperature phase the crystallisation of the poly(ethylene oxide) block influences the spacing of the ordered phase

Multi-scale processes of beech wood disintegration and pretreatment with 1-ethyl-3-methylimidazolium acetate/water mixtures

Background: The valorization of biomass for chemicals and fuels requires efficient pretreatment. One effective strategy involves the pretreatment with ionic liquids which enables enzymatic saccharification of wood within a few hours under mild conditions. This pretreatment strategy is, however, limited by water and the ionic liquids are rather expensive. The scarce understanding of the involved effects, however, challenges the design of alternative pretreatment concepts. This work investigates the multi length-scale effects of pretreatment of wood in 1-ethyl-3-methylimidazolium acetate (EMIMAc) in mixtures with water using spectroscopy, X-ray and neutron scattering. Results: The structure of beech wood is disintegrated in EMIMAc/water mixtures with a water content up to 8.6 wt%. Above 10.7 wt%, the pretreated wood is not disintegrated, but still much better digested enzymatically compared to native wood. In both regimes, component analysis of the solid after pretreatment shows an extraction of few percent of lignin and hemicellulose. In concentrated EMIMAc, xylan is extracted more efficiently and lignin is defunctionalized. Corresponding to the disintegration at macroscopic scale, SANS and XRD show isotropy and a loss of crystallinity in the pretreated wood, but without distinct reflections of type II cellulose. Hence, the microfibril assembly is decrystallized into rather amorphous cellulose within the cell wall. Conclusions: The molecular and structural changes elucidate the processes of wood pretreatment in EMIMAc/water mixtures. In the aqueous regime with >10.7 wt% water in EMIMAc, xyloglucan and lignin moieties are extracted, which leads to coalescence of fibrillary cellulose structures. Dilute EMIMAc/water mixtures thus resemble established aqueous pretreatment concepts. In concentrated EMIMAc, the swelling due to decrystallinization of cellulose, dissolution of cross-linking xylan, and defunctionalization of lignin releases the mechanical stress to result in macroscopic disintegration of cells. The remaining cell wall constituents of lignin and hemicellulose, however, limit a recrystallization of the solvated cellulose. These pretreatment mechanisms are beyond common pretreatment concepts and pave the way for a formulation of mechanistic requirements of pretreatment with simpler pretreatment liquors. © 2016 Viell et al

Probing structural relaxation in complex fluids by critical fluctuations

Complex fluids, such as polymer solutions and blends, colloids and gels, are of growing interest in fundamental and applied soft-condensed-matter science. A common feature of all such systems is the presence of a mesoscopic structural length scale intermediate between atomic and macroscopic scales. This mesoscopic structure of complex fluids is often fragile and sensitive to external perturbations. Complex fluids are frequently viscoelastic (showing a combination of viscous and elastic behaviour) with their dynamic response depending on the time and length scales. Recently, non-invasive methods to infer the rheological response of complex fluids have gained popularity through the technique of microrheology, where the diffusion of probe spheres in a viscoelastic fluid is monitored with the aid of light scattering or microscopy. Here we propose an alternative to traditional microrheology that does not require doping of probe particles in the fluid (which can sometimes drastically alter the molecular environment). Instead, our proposed method makes use of the phenomenon of "avoided crossing" between modes associated with the structural relaxation and critical fluctuations that are spontaneously generated in the system.Comment: 4 pages, 4 figure

InAs nanowire hot-electron Josephson transistor

At a superconductor (S)-normal metal (N) junction pairing correlations can "leak-out" into the N region. This proximity effect [1, 2] modifies the system transport properties and can lead to supercurrent flow in SNS junctions [3]. Recent experimental works showed the potential of semiconductor nanowires (NWs) as building blocks for nanometre-scale devices [4-7], also in combination with superconducting elements [8-12]. Here, we demonstrate an InAs NW Josephson transistor where supercurrent is controlled by hot-quasiparticle injection from normal-metal electrodes. Operational principle is based on the modification of NW electron-energy distribution [13-20] that can yield reduced dissipation and high-switching speed. We shall argue that exploitation of this principle with heterostructured semiconductor NWs opens the way to a host of out-of-equilibrium hybrid-nanodevice concepts [7, 21].Comment: 6 pages, 6 color figure

Retrospective analysis of antimicrobial resistance and bacterial spectrum of infection in Gabon, Central Africa

Background: Physicians depend on reliable information on the local epidemiology of infection and antibiotic resistance rates to guide empiric treatment in critically ill patients. As these data are scarce for Central Africa, we performed a retrospective analysis of microbiological findings from a secondary care hospital in Gabon. Methods: Microbiological reports from 2009 to 2012 were used to assess the non-susceptibility rates of the three most common isolates from six major types of infections (bloodstream, ear-eye-nose-throat, surgical site, skin and soft tissue, urinary tract and wound infection). Results: A high diversity of pathogens was found, but Staphylococcus aureus was predominant in the majority of infections. Overall, the three most prevalent pathogens in children were S. aureus (33.7%), Streptococcus pyogenes (8.1%) and Escherichia coli (4.5%) and in adults S. aureus (23.5%), E. coli (15.1%) and Klebsiella pneumoniae (7.4%). In total, 5.8% (n = 19) of all S. aureus isolates were methicillin resistant. The proportion of extended-spectrum beta-lactamase (ESBL) producing Enterobacteriaceae was 15.4% (n = 78), 49.4% of all K. pneumoniae were ESBL-producer (n = 42). Conclusion: The high diversity of potential pathogens and high resistance rates in Gram-negative bacteria challenge a rational empiric use of antibiotics. Countrywide continuous sentinel surveillance is therefore urgently needed.<br

Dielectric relaxations of nanocomposites composed of HEUR polymers and magnetite nanoparticles

We investigate the dynamics of nanocomposites composed of hydrophobically modified ethoxylated urethanes (HEUR) and magnetite nanoparticles (MNPs) as dry films. Weemployed dielectric relaxation spectroscopy (DRS) in combination with differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC).The three techniques reveal a strong heterogeneity of the matrix of the nanocomposites, consisting of (i) a crystalline poly(ethyleneoxide) PEO bulk phase, (ii) an amorphous PEO portion, and (iii) small PEO crystallites which experience different constraints than the PEO bulk phase. TSDC and DRS reveal a very high direct current (DC)-conductivity of the pure matrix, which increases with MNPs concentration. The increase of the DCconductivity is not related to an increase of the segmental mobility, but most likely to the change of the morphology of the hydrophobic domains of the polymer matrix, due to the formation of large MNPs clusters. Indeed, the MNPs neither influence the segmental dynamics of the polymer nor the phase behavior of the polymer matrix. The addition of MNPs slightly increases the activation energy related to the γ-relaxation of the polymer. This effect might be related to the changes in nano-morphology as demonstrated by the slight increase of the degree of crystallinity. The analysis of the DRS data with the electrical modulus M’’(ω) and the derivative ε’’der formalism allow us to identify a low-frequency process in addition to the conductivity relaxation. This low-frequency dispersion is also revealed by TSDC. It is most likely related to the Maxwell-Wagner- Sillars relaxation, which typically occurs in systems which feature phase separation. The detailed investigation of the dielectric properties of these novel nanocomposites with increasing MNPs concentration will be useful for their practical application, for example as absorbers of electromagnetic waves

Response of a Li-glass/multi-anode photomultiplier detector to collimated thermal-neutron beams

The response of a position-sensitive Li-glass scintillator detector being developed for thermal-neutron detection with 6 mm position resolution has been investigated using collimated beams of thermal neutrons. The detector was moved perpendicularly through the neutron beams in 0.5 to 1.0 mm horizontal and vertical steps. Scintillation was detected in an 8 X 8 pixel multi-anode photomultiplier tube on an event-by-event basis. In general, several pixels registered large signals at each neutron-beam location. The number of pixels registering signal above a set threshold was investigated, with the maximization of the single-hit efficiency over the largest possible area of the detector as the primary goal. At a threshold of ~50% of the mean of the full-deposition peak, ~80% of the events were registered in a single pixel, resulting in an effective position resolution of ~5 mm in X and Y. Lower thresholds generally resulted in events demonstrating higher pixel multiplicities, but these events could also be localized with ~5 mm position resolution.Comment: 23 pages, 8 figure

Response of a Li-glass/multi-anode photomultiplier detector to α-particles from ²⁴¹Am

The response of a position-sensitive Li-glass scintillator detector to -particles from a collimated ²⁴¹Am source scanned across the face of the detector has been measured. Scintillation light was read out by an 8 x 8 pixel multi-anode photomultiplier and the signal amplitude for each pixel has been recorded for every position on a scan. The pixel signal is strongly dependent on position and in general several pixels will register a signal (a hit) above a given threshold. The effect of this threshold on hit multiplicity is studied, with a view to optimize the single-hit efficiency of the detector