To Sandwich Technetium: Highly Functionalized Bis-Arene Complexes [99mTc(η6-arene)2]+ Directly from Water and [99mTcO4]−

The labeling of (bio)molecules with metallic radionuclides such as ^99mTc demands conjugated, multidentate chelators. However, this is not always necessary since phenyl rings can directly serve as integrated, organometallic ligands. Bis-arene sandwich complexes are generally prepared by the Fischer–Hafner reaction. In extension of this, we show that [^99mTc(η⁶-C₆R₆)₂]⁺-type complexes are directly accessible from water and [^99mTcO₄]⁻, even using arenes incompatible with Fischer–Hafner conditions. To unambiguously confirm the nature of these unprecedented ^99mTc complexes, their rhenium homologous have been prepared by substituting naphthalene ligands in [Re(η⁶-C₁₀H₈)₂]⁺ with the corresponding phenyl groups. The ease with which highly stable [^99mTc(η⁶-C₆R₆)₂]⁺ complexes are formed under standard labeling conditions enables a multitude of new potential imaging agents based on commercial pharmaceuticals or lead structures.     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.     

Back to the future: A retrospective assessment of model‐based scenarios for the management of the shrimp fishery in French Guiana facing global change

While the number of models dedicated to predicting the consequences of alternative resource management strategies has increased, instances in which authors look back at past predictions to learn from discrepancies between these and observed developments are scarce. In the past decades, the French Guiana shrimp fishery has experienced shrimp market globalization and decreasing levels of shrimp recruitment due to environmental changes. In 2006, a bio‐economic model of this fishery was developed to simulate its possible responses to economic and environmental scenarios up to 2016. Here, we compare here these predictions to the observed trajectories. While the number of active vessels corresponds to that which was predicted, the estimated shrimp stock does not. Important driving factors had not been anticipated, including a general strike, natural disasters, and the end of the global financial crisis. These results show the importance of participative approaches involving stakeholders in the co‐construction and shared representation of scenarios. Recommendations for resource managers

• Effective fisheries resources management and a fortiori, the capacity of the fisheries to adapt to global change, requires understanding of both ecological and economics dynamics.
• The temporal trajectory of the trawling shrimp fisheries has been well monitored, and the decline of both stock and fleet is understood regarding ecological and economic changes: Changes in the environmental conditions of shrimp recruitment, and oil price increase and selling price decrease.
• However, our bio‐economic modeling work showed that, even with a good understanding of the dynamics explaining past trajectories, unpredictable events (strike, natural disasters…) have acted as other key driving factors altering the capacity of the model to represent possible futures.
• These results led us to recommend a better integration of the expertise of social and political scientists in developing models of bio‐economic systems to increase the quality of scenario predictions, and to argue for more participative approaches involving the stakeholders.

     

Highlights on the Binding of Cobalta-Bis-(Dicarbollide) with Glucose Units

Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C₂B₉H₁₁)₂]⁻, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations.     

Uncertainty quantification in a chemical system using error estimate-based mesh adaption

This paper describes a rigorous a posteriori error analysis for the stochastic solution of non-linear uncertain chemical models. The dual-based a posteriori stochastic error analysis extends the methodology developed in the deterministic finite elements context to stochastic discretization frameworks. It requires the resolution of two additional (dual) problems to yield the local error estimate. The stochastic error estimate can then be used to adapt the stochastic discretization. Different anisotropic refinement strategies are proposed, leading to a cost-efficient tool suitable for multi-dimensional problems of moderate stochastic dimension. The adaptive strategies allow both for refinement and coarsening of the stochastic discretization, as needed to satisfy a prescribed error tolerance. The adaptive strategies were successfully tested on a model for the hydrogen oxidation in supercritical conditions having 8 random parameters. The proposed methodologies are however general enough to be also applicable for a wide class of models such as uncertain fluid flows.     

Alkoxyallene‐ynes: Selective Preparation of Bicyclo[5.3.0] Ring Systems Including a δ‐Alkoxy Cyclopentadienone

The development of an intramolecular rhodium(I)‐catalyzed Pauson–Khand reaction of alkoxyallene‐ynes with a proximal alkoxy group is reported. This reaction, in the presence of a [Rh(cycloocta‐1,5‐diene)Cl]₂/propane‐1,3‐diylbis(diphenylphosphane) system under a CO atmosphere, constitutes a powerful tool for selectively accessing carbo‐ and heterobicyclo[5.3.0] frameworks featuring an enol ether moiety. Through this procedure, a straightforward access to guaiane skeletons with a tertiary hydroxy group at the C10 position was achieved.