Copper‐Mediated Formation of Aryl,Heteroaryl, Vinyl and Alkynyl Difluoromethylphosphonates: A General Approach to Fluorinated Phosphate Mimics

A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF₂PO(OEt)₂, iodonium salts and a copper salt provided a straightforward manifold to reach these highly relevant products. The reaction proved to be highly functional group tolerant and proceeded under mild conditions, giving the corresponding products in good to excellent yields. This method represents the first general synthetic route to this important class of fluorinated scaffolds, which are well‐recognized as in vivo stable phosphate surrogates.     

Flow instability and shear localization in a drilling mud

To have a better knowledge of problems occurring with drilling fluids in complex wells, we carried out a detailed rheological analysis of a typical drilling mud at low shear rates using both conventional rheometry and MRI velocimetry. We show the existence of a viscosity bifurcation effect: Below a critical stress value, the mud tends to completely stop flowing, whereas beyond this critical stress, it reaches an apparent shear rate larger than a finite (critical) value, and no stable flows can be obtained between this critical shear rate value and zero. These results are confirmed by MRI velocity profiles, which exhibit a slope break at the interface between the solid and the liquid phases inside the Couette geometry. Moreover, this viscosity bifurcation is a transient phenomenon, the progressive development of which can be observed by MRI. A further examination of MRI data shows that, in the transient regime, the shear rate does not vary monotonously in the rheometer gap and is particularly large along the outer (rough) cylinder, which might be at the origin of the development of a region of constant shear rate in the apparent flow curve.     

Experimental and Computational Study on the Anti-Markovnikov Hydrofunctionalization of Olefins Using Glycine-Extended AQ-Auxiliaries

Two similar tridentate directing groups derived from glycine and 8-aminoquinoline were shown to enable the palladium-catalyzed anti-Markovnikov hydrofunctionalization of 4-pentenylamine with drastically different efficiencies. A computational investigation into the origin of the reactivity difference between these isomeric, carbonyl-transposed auxiliaries suggests that protonation state, thus charge of the substrate-metal complex prior to nucleopalladation is key. These investigations have culminated in a directing group design that can undergo Pd-catalyzed hydrofunctionalization under relatively mild conditions, as low as room temperature.     

Load balancing via random local search in closed and open systems

In this paper, we analyze the performance of random load resampling and migration strategies in parallel server systems. Clients initially attach themselves to an arbitrary server, but may switch servers independently at random instants of time in an attempt to improve their service rate. This approach to load balancing contrasts with traditional approaches where clients make smart server selections upon arrival (e.g., Join-the-Shortest-Queue policy and variants thereof). Load resampling is particularly relevant in scenarios where clients cannot predict the load of a server before being actually attached to it. An important example is in wireless spectrum sharing where clients try to share a set of frequency bands in a distributed manner. We first analyze the natural Random Local Search (RLS) strategy. Under this strategy, after sampling a new server randomly, clients only switch to it if their service rate is improved. In closed systems, where the client population is fixed, we derive tight estimates of the time it takes under RLS strategy to balance the load across servers. We then study open systems where clients arrive according to a random process and leave the system upon service completion. In this scenario, we analyze how client migrations within the system interact with the system dynamics induced by client arrivals and departures. We compare the load-aware RLS strategy to a load-oblivious strategy in which clients just randomly switch server without accounting for the server loads. Surprisingly, we show that both load-oblivious and load-aware strategies stabilize the system whenever this is at all possible. We use large-system asymptotics to characterize system performance, and augment this with simulations, which suggest that the average client sojourn time under the load-oblivious strategy is not considerably reduced when clients apply smarter load-aware strategies.     

Stability and linear oscillations of liquid bridges with varied boundary conditions under zero gravity

This article deals with stability and small linear oscillations of liquid bridges between fixed solid surfaces (parallel plates, spheres, ...) under zero gravity. A general investigation method for any kind of axisymmetric liquid bridge is exposed but the author focus his work on the spherical liquid bridge cases. In particular, he exposes a full theoretical study of spherical liquid bridges between two spheres, plates and cones.     

The additive property of the inconsistency degree in intertemporal decision making through the generalization of psychophysical laws

Intertemporal decision making involves choices among options whose effects occur at different moments. These choices are influenced not only by the effect of reward value perception at different moments, but also by the time perception effect. One of the main difficulties that affect standard experiments involving intertemporal choices is the simultaneity of both effects on time discounting. In this paper, we unify the psychophysical laws and discount value functions using the one-parameter exponential and logarithmic functions from nonextensive statistical mechanics. Also, we propose to measure the degree of inconsistency. This quantity allow us to discriminate both effects of time and value perception on discounting process and, by integration, obtain other main quantities like impulsivity and discount functions.     

Solubility and Raman Spectroscopic Study of As(III) Speciation in Organic Compound-Water Solutions. A Hydration Approach for Aqueous Arsenic in Complex Solutions

Solubilities of arsenolite (As₂O₃, cub.) were measured from 22 to 90°C in water–acetone, water–acetic acid, and water—formic acid solutions of compositions ranging from the pure organic compound to pure water. Raman spectra were obtained at ambient temperature on As-containing water–acetic acid and water–acetone solutions. Results show that arsenic solvation by these organic compounds is negligible and hydroxide species dominate As speciation over a wide range of water activity (a_{H 2 O}> 0.01). The solubility data were analyzed using an approach based on stoichiometric hydration reactions. Results show that As₂O₃ solubility can be described as a function of water activity, independently of the nature of the organic compound, by involving two neutral As hydroxide complexes: As(OH)₃ and As(OH)₃·4H₂O. Stability constants derived for these species indicate that hydration weakens with increasing temperature. Calculations using these constants show that at low temperatures the tetrahydrate As(OH)₃·4H₂O is dominant in water-rich solutions; by contrast, in high-temperature crustal fluids, As(OH)₃ becomes the major As species. The proposed hydration model can be used to analyze solubility of arsenic-bearing minerals and arsenic transport in complex H₂O–CO₂—electrolyte solutions encountered in natural and industrial environments.     

High diversity on simple substrates: 1,4-dihalo-2-butenes and other difunctionalized allylic halides for copper-catalyzed S(N)2' reactions

Enantioselective allylic alkylation with an organomagnesium reagent catalyzed by copper thiophene carboxylate (CuTC) was carried out on difunctionalized substrates, such as commercially available 1,4-dichloro-2-butene and 1,4-dibromo-2-butene, and on similar compounds of higher substitution pattern of the olefin for the formation of all-carbon chiral quaternary centers. The high regioselectivity obtained throughout the reactions favored good regiocontrol for the addition of phenyl Grignard reagents. Other difunctionalized substrates (allylic ethers and allylic alcohols) also underwent asymmetric S(N)2' substitution.