Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb,Cs; M = Mo,W) introducing the transition oxometalate hydrides

The four compounds A₃MO₄H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb₃MoO₄D, Cs₃MoO₄D and Cs₃WO₄D crystallize in the antiperovskite-like K₃SO₄F-structure type, while Rb₃WO₄D adopts a different orthorhombic structure. ²H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb₃WO₄H shows a unique, peculiar valence band structure dominated by hydride states.

The synthesis, structures and electronic properties of the first four heteroanionic compounds containing both hydride and transition oxometalate ions are reported.     

Regioselective Synthesis of 5- and 3-Hydroxy-N-Aryl-1H-Pyrazole-4-Carboxylates and Their Evaluation as Inhibitors of Plasmodium falciparum Dihydroorotate Dehydrogenase

In silico evaluation of various regioisomeric 5- and 3-hydroxy-substituted alkyl 1-aryl-1H-pyrazole-4-carboxylates and their acyclic precursors yielded promising results with respect to their binding in the active site of dihydroorotate dehydrogenase of Plasmodium falciparum (PfDHODH). Consequently, four ethyl 1-aryl-5-hydroxy-1H-pyrazole-4-carboxylates and their 3-hydroxy regioisomers were prepared by two-step syntheses via enaminone-type reagents or key intermediates. The synthesis of 5-hydroxy-1H-pyrazoles was carried out using the literature protocol comprising acid-catalyzed transamination of diethyl [(dimethylamino)methylene]malonate with arylhydrazines followed by base-catalyzed cyclization of the intermediate hydrazones. For the synthesis of isomeric methyl 1-aryl-3-hydroxy-1H-pyrazole-4-carboxylates, a novel two-step synthesis was developed. It comprises acylation of hydrazines with methyl malonyl chloride followed by cyclization of the hydrazines with tert-butoxy-bis(dimethylamino)methane. Testing the pyrazole derivatives for the inhibition of PfDHODH showed that 1-(naphthalene-2-yl)-5-hydroxy-1H-pyrazole-4-carboxylate and 1-(naphthalene-2-yl)-, 1-(2,4,6-trichlorophenyl)-, and 1-[4-(trifluoromethyl)phenyl]-3-hydroxy-1H-pyrazole-4-carboxylates (~30% inhibition) were slightly more potent than a known inhibitor, diethyl α-{[(1H-indazol-5-yl)amino]methylidene}malonate (19% inhibition).     

REACTION OF LITHIUM DERIVATIVE OF DIETHYL PHENYLMETHANE-PHOSPHONATE WITH KETONES

Abstract

The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time.     

Introduction and Analysis of a Method for the Investigation of QCD-like Tree Data

The properties of decays that take place during jet formation cannot be easily deduced from the final distribution of particles in a detector. In this work, we first simulate a system of particles with well-defined masses, decay channels, and decay probabilities. This presents the “true system” for which we want to reproduce the decay probability distributions. Assuming we only have the data that this system produces in the detector, we decided to employ an iterative method which uses a neural network as a classifier between events produced in the detector by the “true system” and some arbitrary “test system”. In the end, we compare the distributions obtained with the iterative method to the “true” distributions.     

Multifractality in Quasienergy Space of Coherent States as a Signature of Quantum Chaos

We present the multifractal analysis of coherent states in kicked top model by expanding them in the basis of Floquet operator eigenstates. We demonstrate the manifestation of phase space structures in the multifractal properties of coherent states. In the classical limit, the classical dynamical map can be constructed, allowing us to explore the corresponding phase space portraits and to calculate the Lyapunov exponent. By tuning the kicking strength, the system undergoes a transition from regularity to chaos. We show that the variation of multifractal dimensions of coherent states with kicking strength is able to capture the structural changes of the phase space. The onset of chaos is clearly identified by the phase-space-averaged multifractal dimensions, which are well described by random matrix theory in a strongly chaotic regime. We further investigate the probability distribution of expansion coefficients, and show that the deviation between the numerical results and the prediction of random matrix theory behaves as a reliable detector of quantum chaos.     

Creep deformation at crack tips in elastic-viscoplastic solids

The evaluation of crack growth tests under creep conditions must be based on the stress analysis of a cracked body taking into account elastic, plastic and creep deformation. In addition to the well-known analysis of a cracked body creeping in secondary (steady-state) creep, the stress field at the tip of a stationary crack is calculated for primary (strain-hardening) or tertiary (strain-softening) creep of the whole specimen. For the special hardening creep-law considered, a path-independent integral C¹_h, can be defined which correlates the near-tip field to the applied load.It is also shown how, after sudden load application, creep strains develop in the initially elastic or, for a higher load level, plastic body. Characteristic times are derived to distinguish between short times when the creep-zones, in which creep strains are concentrated, are still small, and long times when the whole specimen creeps extensively in primary and finally in secondary and tertiary creep. Comparing the creep-zone sizes with the specimen dimensions or comparing the characteristic times with the test duration, one can decide which deformation mechanism prevails in the bulk of the specimen and which load parameter enters into the near-tip stress field and determines crack growth behavior. The governing load parameter is the stress intensity factor K₁ if the bulk of the specimen is predominantly elastic and it is the J-integral in a fully-plastic situation when large creep strains are still confined to a small zone. The C¹_h-integral applies if the bulk of the specimen deforms in primary or tertiary creep, and C¹ is the relevant load parameter for predominantly secondary creep of the whole specimen.     

An expansion formula for fractional derivatives of variable order

In this work we extend our previous results and derive an expansion formula for fractional derivatives of variable order. The formula is used to determine fractional derivatives of variable order of two elementary functions. Also we propose a constitutive equation describing a solidifying material and determine the corresponding stress relaxation function.     

Autoionization mediated by electron transfer

Electron-electron coincidence spectra of Ar-Kr clusters after photoionization have been measured. An electron with the kinetic energy range from 0 to approximately 1 eV is found in coincidence with the Ar 3s cluster photoelectron. The low kinetic energy electron can be attributed to an Ar + Kr+ + Kr+ final state which forms after electron transfer mediated decay. This autoionization mechanism results from a concerted transition involving three different atoms in a van der Waals cluster; it was predicted theoretically, but hitherto not observed.     

Accumulation of Stark-decelerated NH molecules in a magnetic trap

Here we report on the accumulation of ground-state NH molecules in a static magnetic trap. A pulsed supersonic beam of NH (a¹Δ) radicals is produced and brought to a near standstill at the center of a quadrupole magnetic trap using a Stark decelerator. There, optical pumping of the metastable NH radicals to the X³Σ^? ground state is performed by driving the spin-forbidden A³Π ← a¹Δ transition, followed by spontaneous A → X emission. The resulting population in the various rotational levels of the ground state is monitored via laser induced fluorescence detection. A substantial fraction of the ground-state NH molecules stays confined in the several milliKelvin deep magnetic trap. The loading scheme allows one to increase the phase-space density of trapped molecules by accumulating packets from consecutive deceleration cycles in the trap. In the present experiment, accumulation of six packets is demonstrated to result in an overall increase of only slightly over a factor of two, limited by the trap-loss and reloading rates.