Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An(IV)((Ar)acnac)(4) Complexes (An = Th, U, Np, Pu; (Ar)acnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-(t)Bu(2)C(6)H(3))

A series of tetravalent An(IV) complexes with a bis-phenyl β-ketoiminate N,O donor ligand has been synthesized with the aim of identifying bonding trends and changes across the actinide series. The neutral molecules are homoleptic with the formula An((Ar)acnac)(4) (An = Th (1), U (2), Np (3), Pu (4); (Ar)acnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-(t)Bu(2)C(6)H(3)) and were synthesized through salt metathesis reactions with actinide chloride precursors. NMR and electronic absorption spectroscopy confirm the purity of all four new compounds and demonstrate stability in both solution and the solid state. The Th, U, and Pu complexes were structurally elucidated by single-crystal X-ray diffraction and shown to be isostructural in space group C2/c. Analysis of the bond lengths reveals shortening of the An-O and An-N distances arising from the actinide contraction upon moving from 1 to 2. The shortening is more pronounced upon moving from 2 to 4, and the steric constraints of the tetrakis complexes appear to prevent the enhanced U-O versus Pu-O orbital interactions previously observed in the comparison of UI(2)((Ar)acnac)(2) and PuI(2)((Ar)acnac)(2) bis-complexes. Computational analysis of models for 1, 2, and 4 (1a, 2a, and 4a, respectively) concludes that both the An-O and the An-N bonds are predominantly ionic for all three molecules, with the An-O bonds being slightly more covalent. Molecular orbital energy level diagrams indicate the largest 5f-ligand orbital mixing for 4a (Pu), but spatial overlap considerations do not lead to the conclusion that this implies significantly greater covalency in the Pu-ligand bonding. QTAIM bond critical point data suggest that both U-O/U-N and Pu-O/Pu-N are marginally more covalent than the Th analogues.     

Lactate Biosensor Based on the Adsorption of Polyelectrolyte Stabilized Lactate Oxidase into Porous Conductive Carbon

 In this work the development a lactate biosensor is illustrated. Lactate oxidase is stabilized with the cationic polyelectrolyte diethylaminoethyl-dextran, and the resulting enzyme-polyelectrolyte complexes are physically absorbed into a highly porous and conductive carbon electrode for the construction of the biosensor. The amount of diethylaminoethyl-dextran used is optimized with respect to the sensor sensitivity and stability. Optimum results obtained with enzyme solution containing 0.5% w/v diethylaminoethyl-dextran and 200 U/ml lactate oxidase. The resulting biosensors present increased operational (over 240 hours of continuous polarization) and storage stability (more than 5 months), while the reproducibility was calculated to be better than 5.0% RSD.     

Chemfet Based Microsensors Covered with Ion-Partitioning Polymeric Membranes

 The development of a new type of microsensors based on chemically sensitive field-effect transistors (CHEMFETs) covered with polymeric bulk ion-partitioning membranes is presented. For the construction of the microsensor, a PVC plasticized membrane containing two ionophores, one selective to protons and the other to the analyte cation of interest, is placed on the gate of a pH sensitive field-effect transistor which acts as the transducer. With the use of thin (5–10 μm) ion-partitioning membranes onto the pH-sensitive ISFET gate, the proton displacement out of the membrane and to the pH sensitive gate is fast and reversible. This displacement generates a signal that is directly related to the analyte concentration found in the test solution. Comparing the performance of CHEMFETs and ISEs selective to the monovalent potassium cation and the divalent calcium ion validates this novel CHEMFET response mechanism.     

Oxodealkenylative Cleavage of Alkene C(sp3)−C(sp2) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials

Reported herein is a one‐pot protocol for the oxodealkenylative introduction of carbonyl functionalities into terpenes and terpene‐derived compounds. This transformation proceeds by Criegee ozonolysis of an alkene, reductive cleavage of the resulting α‐alkoxy hydroperoxide, trapping of the generated alkyl radical with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO), and subsequent oxidative fragmentation with MMPP. Using readily available starting materials from chiral pool, a variety of carbonyl‐containing products have been accessed rapidly in good yields.     

Analytical calculation of in-plane response of plates with concentrated masses to impact and application to pyroshock simulation

In aerospace missions pyroshocks occur due to controlled explosions of ordnance devices enabling the functionality of space modules. These shocks result from deployment mechanisms or opening solar sails and can cause failures of electronic devices and structures. Thus, essential components for assuring the reliability of modules are pyroshock tests for the completion of which strict requirements by the aerospace administrations have to be met. One of them is the definition of a specific acceleration signal and, based on this, the Shock Response Spectrum (SRS) for each part.So far, there is rather empirical than analytical knowledge about producing desired SRS with mechanical impacts and its characteristics due to the variation of input parameters. In this paper a widespread testing procedure for far-field pyroshocks is discussed which is realized by the in-plane impact of a hammer pendulum on a plate including the test specimen. The mechanical model consists of the contact between a rigid sphere and a free deformable rectangular plate with attached masses including subsequent propagation and reflection of longitudinal waves. In order to allow for a prediction of the acceleration field and the corresponding SRS due to the impact the problem is solved semi-analytically by using Hertzian contact theory, the Galerkin-procedure and numerical integration in time domain. The in-plane problem has, to the best of the authors' knowledge, not yet been treated in the literature in the way presented.The results calculated are compared with experimental data showing very good coincidence and allowing for a fast prediction of far-field pyroshock tests due to the impact excitation by a hammer pendulum. Hence, the framework of this paper is an enrichment for the current state of the art considering analytical pyroshock simulation. By better understanding the effect of pyroshocks to one and two dimensional structures a reduction of costs as well as durations for testing procedures seems promising.     

Linear variance bounds for particle approximations of time-homogeneous Feynman–Kac formulae

This article establishes sufficient conditions for a linear-in-time bound on the non-asymptotic variance for particle approximations of time-homogeneous Feynman–Kac formulae. These formulae appear in a wide variety of applications including option pricing in finance and risk sensitive control in engineering. In direct Monte Carlo approximation of these formulae, the non-asymptotic variance typically increases at an exponential rate in the time parameter. It is shown that a linear bound holds when a non-negative kernel, defined by the logarithmic potential function and Markov kernel which specify the Feynman–Kac model, satisfies a type of multiplicative drift condition and other regularity assumptions. Examples illustrate that these conditions are general and flexible enough to accommodate two rather extreme cases, which can occur in the context of a non-compact state space: (1) when the potential function is bounded above, not bounded below and the Markov kernel is not ergodic; and (2) when the potential function is not bounded above, but the Markov kernel itself satisfies a multiplicative drift condition.