Reductive Elimination at Pb(II) Center of an (Amino)plumbylene-Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis

A stable (amino)plumbylene-substituted phosphaketene 3 was synthesized by the successive reactions of PbCl₂ with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3 , at 80 °C, leads to the transient formation of corresponding amino- and phosphanylidene-phosphaketenes ( 6 and 7 ), via a reductive elimination at the Pb^II center forming new N−P and P−P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4 , which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access.     

Particle paths in Stokes’ edge wave

We treat the particle motion in Stokes’ linear edge wave along a uniformly sloping beach. By a rotation of the coordinate frame, we show that there is no particle motion in the direction orthogonal to the sloping beach, and conclude that particles have a longshore drift in the direction of wave propagation which decreases with depth and distance from the shoreline. We discuss the application of this rotated coordinate frame to higher mode (Ursell) and weakly nonlinear (Whitham) edge waves, and show that the weakly nonlinear case is identical to that for two-dimensional deep-water Stokes waves.     

Pentafluorophenyl Ester‐based Polymersomes as Nanosized Drug‐Delivery Vehicles

In this work, activated ester chemistry is employed to synthesize biocompatible and readily functionalizable polymersomes. Via aminolysis of pentafluorophenyl methacrylate‐based precursor polymers, an N‐(2‐hydroxypropyl) methacrylamide (HPMA)‐analog hydrophilic block is obtained. The precursor polymers can be versatile functionalized by simple addition of suitable primary amines during aminolysis as demonstrated using a fluorescent dye. Vesicle formation is proven by cryoTEM and light scattering. High encapsulation efficiencies for hydrophilic cargo like siRNA are achieved using dual centrifugation and safe encapsulation is demonstrated by gel electrophoresis. In vitro studies reveal low cytotoxicity and no protein adsorption‐induced aggregation in human blood serum occurs, making the vesicles interesting candidates as nanosized drug carriers.

     

Partially Observable Markov Decision Processes incorporating epistemic uncertainties

The use of Markov Decision Processes for Inspection Maintenance and Rehabilitation of civil engineering structures relies on the use of several transition matrices related to the stochastic degradation process, maintenance actions and imperfect inspections. Point estimators for these matrices are usually used and they are evaluated using statistical inference methods and/or expert evaluation methods. Thus, considerable epistemic uncertainty often veils the true values of these matrices. Our contribution through this paper is threefold. First, we present a methodology for incorporating epistemic uncertainties in dynamic programming algorithms used to solve finite horizon Markov Decision Processes (which may be partially observable). Second, we propose a methodology based on the use of Dirichlet distributions which answers, in our sense, much of the controversy found in the literature about estimating Markov transition matrices. Third, we show how the complexity resulting from the use of Monte-Carlo simulations for the transition matrices can be greatly overcome in the framework of dynamic programming. The proposed model is applied to concrete bridge under degradation, in order to provide the optimal strategy for inspection and maintenance. The influence of epistemic uncertainties on the optimal solution is underlined through sensitivity analysis regarding the input data.     

2‐Hydroxyazobenzenes to Tailor pH Pulses and Oscillations with Light

This paper evaluates the 2‐hydroxyazobenzene platform for tailoring proton concentration pulses and oscillations with monochromatic light. The easily prepared 2‐hydroxyazobenzenes exhibit large absorptions in the near‐UV range. Photoisomerization was investigated by UV/Vis absorption, ¹H NMR spectroscopy, and steady‐state fluorescence emission. In the whole investigated series, the trans stereoisomer of the 2‐hydroxyazobenzene motif provides the corresponding cis derivative with an action cross section in the 10³ M ^?1 cm^?1 range. At the same time, photoisomerization is accompanied by a significant pK drop of the phenol group. According to the phenyl‐substituent pattern, cis‐to‐trans thermal back‐isomerization can be tuned in the 10 ms–100 s range. Up to 2 units of reversible pH drops or pH oscillations on the 10 s timescale have been obtained by appropriately tailoring single‐wavelength illumination of 2‐hydroxyazobenzene solutions.