Step and steady shear responses of nearly monodisperse highly entangled 1,4-polybutadiene solutions

Nonlinear relaxation dynamics of highly entangled solutions of high molecular weight 1,4-polybutadiene (PB) in a PB oligomer are studied in steady shear and step shear flows. Polymer entanglement densities vary in the range 14hN/N_e(J)⣴, allowing systematic investigation of entanglement effects on nonlinear rheological response. In agreement with previous steady shear studies using well entangled polystyrene solutions, a flow regime is found where both the steady-state shear stress and first normal stress difference remain constant or increase quite slowly with shear rate, leading to a plateau in the steady-state orientation angle. The magnitude of the average orientation angle in the plateau range is in accordance with predictions of a recent theory by Islam and Archer (2001). In step shear, the nonlinear relaxation modulus G(t,%) is approximately factorable into time-dependent G(t) and strain-dependent h(%) functions only at long times, t>5_k, where 5_k,O(F_d0). This finding is consistent with earlier observations for entangled polystyrene solutions; however the complex crossing pattern in G(t,%)h^-1(%) that precede factorability in the latter materials is not observed. For all but the most entangled sample, apparent shear damping functions h (%,t)=(G(t,%))/(G(t)) immediately following imposition of shear are in nearly quantitative accord with the damping function h_DEIA predicted by Doi-Edwards theory.     

Proton Intercalation/De-Intercalation Dynamics in Vanadium Oxides for Aqueous Aluminum Electrochemical Cells

Understanding cation (H⁺, Li⁺, Na⁺, Al³⁺, etc.) intercalation/de-intercalation chemistry in transition metal compounds is crucial for the design of cathode materials in aqueous electrochemical cells. Here we report that orthorhombic vanadium oxides (V₂O₅) supports highly reversible proton intercalation/de-intercalation reactions in aqueous media, enabling aluminum electrochemical cells with extended cycle life. Empirical analyses using vibrational and x-ray spectroscopy are complemented with theoretical analysis of the electrostatic potential to establish how and why protons intercalate in V₂O₅ in aqueous media. We show further that cathode coatings composed of cation selective membranes provide a straightforward method for enhancing cathode reversibility by preventing anion cross-over in aqueous electrolytes. Our work sheds light on the design of cation transport requirements for high-energy reversible cathodes in aqueous electrochemical cells.     

Assessment of Reproducibility of Laser Electrospray Mass Spectrometry using Electrospray Deposition of Analyte

A nonresonant, femtosecond (fs) laser is employed to desorb samples of Victoria blue deposited on stainless steel or indium tin oxide (ITO) slides using either electrospray deposition (ESD) or dried droplet deposition. The use of ESD resulted in uniform films of Victoria blue whereas the dried droplet method resulted in the formation of a ring pattern of the dye. Laser electrospray mass spectrometry (LEMS) measurements of the ESD-prepared films on either substrate were similar and revealed lower average relative standard deviations for measurements within-film (20.9%) and between-films (8.7%) in comparison to dried droplet (75.5% and 40.2%, respectively). The mass spectral response for ESD samples on both substrates was linear (R²?>?0.99), enabling quantitative measurements over the selected range of 7.0?×?10^?11 to 2.8?×?10^?9 mol, as opposed to the dried droplet samples where quantitation was not possible (R²?=?0.56). The limit of detection was measured to be 210 fmol.

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Syntheses of 2‐Keto‐3‐deoxy‐D‐xylonate and 2‐Keto‐3‐deoxy‐L‐arabinonate as Stereochemical Probes for Demonstrating the Metabolic Promiscuity of Sulfolobus solfataricus Towards D‐Xylose and L‐Arabinose

Practical syntheses of 2‐keto‐3‐deoxy‐D ‐xylonate (D ‐KDX) and 2‐keto‐3‐deoxy‐L ‐arabinonate (L ‐KDA) that rely on reaction of the anion of ethyl 2‐[(tert‐butyldimethylsilyl)oxy]‐2‐(dimethoxy phosphoryl) acetate with enantiopure glyceraldehyde acetonide, followed by global deprotection of the resultant O‐silyl‐enol esters, have been developed. This has enabled us to confirm that a 2‐keto‐3‐deoxy‐D ‐gluconate aldolase from the archaeon Sulfolobus solfataricus demonstrates good activity for catalysis of the retro‐aldol cleavage of both these enantiomers to afford pyruvate and glycolaldehyde. The stereochemical promiscuity of this aldolase towards these enantiomeric aldol substrates confirms that this organism employs a metabolically promiscuous pathway to catabolise the C5‐sugars D ‐xylose and L ‐arabinose.     

Oil in Louisiana''''s estuarine environments: A development model

Coastal erosion, accelerated by sea level rise, and subsidence are major Louisiana issues. With current sea-level-rise projections, coupled with the state's eroding barrier islands and coastal wetlands, the region's estuarine environments are in jeopardy of being lost, redefined, or permanently altered. As the coast erodes, Louisiana is endangered of losing valuable wetland's habitat. In addition, if the barrier islands disappear, the region's wetland-oriented oil and gas wells and associated infrastructure will be at risk to open Gulf conditions. If this should occur, each well, pipeline, and storage battery represents a potential environmental catastrophe.     

Displacement Uncertainty Quantifications in T3-Stereocorrelation

Background Uncertainty quantifications are required for any measurement result to be meaningful.

Objective The present work aims at deriving and comparing a priori estimates of displacement uncertainties in T3-stereocorrelation for a setup to perform high temperature tests.

Methods Images acquired prior to the actual experiment (i.e.,at room temperature) were registered using 3-noded triangular elements (T3-stereocorrelation) to determine displacement uncertainties for different positions of the experimental setup.

Results The displacement uncertainties were then compared to their a priori estimates.

Conclusions For the analyzed experiment, it is shown that noise floor estimates only differed by a factor 2 when compared to a posteriori measurements of standard displacement uncertainties.

     

An adaptive control scheme for a continuous plant under Known output delay, unmodelled dynamics, and input saturation

This paper deals with robustness of adaptive control of continuoussystems subject to known output delay, input saturation, unmodelledlinear dynamics, and bounded disturbances. A simple gradient-typealgorithm with a relative deadzone is used. The relative deadzoneis built with an estimated contribution of the unmodelled dynamicsto the system output. The basic tool used for stability androbustness analysis is Gronwall's lemma.