Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1JCF coupling constants in fluorobenzene derivatives

Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of (1)J(CF) NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH(2); NO(2)) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for (1)J(CF) spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the (1)J(CF) with those observed for the SOPPA(CCSD) method was obtained. The (1)J(CF) SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to (1)J(CF) SSCCs is discussed.     

Computational study on the anomalous fluorescence behavior of isoflavones

Isoflavones are known to show fluorescence with intensities that depend strongly on the solvent properties and exhibit Stokes' shifts as large as 1.4 eV. While some of this behavior can be explained by (excited state) deprotonation, this mechanism does not apply for all isoflavones. The aim of this study is to computationally and experimentally investigate the reasons for this anomalous behavior of neutral isoflavones, taking the daidzein molecule as a model compound. We find that the absence in fluorescence in aprotic solvents and the weak fluorescence in protic solvents can be explained by a change of order of the lowest singlet states in which a fluorescent charge-transfer state lies below the nonfluorescent locally excited state in water but not in acetonitrile. The large Stokes' shift is partly due to a significant rotation among the chromone-phenyl bond in the excited state.     

Existence and asymptotic behavior for elliptic equations with singular anisotropic potentials

We study the equation Δu+u|u|^p−1+V(x)u+f(x)=0 in Rn, where n?3 and p>n/(n−2). The forcing term f and the potential V can be singular at zero, change sign and decay polynomially at infinity. We can consider anisotropic potentials of form h(x)|x|⁻² where h is not purely angular. We obtain solutions u which blow up at the origin and do not belong to any Lebesgue space Lr. Also, u is positive and radial, in case f and V are. Asymptotic stability properties of solutions, their behavior near the singularity, and decay are addressed.     

Reactivity of Pd3(dppm)3(CO)n+ and Pd3(dppm)3(CO)(RCCR)n+ (n?=?0, +1, +2) Towards F?. Evidence of Reactive Intermediates and X-Ray Structure of [Pd3(dppm)3(MeO2CC≡CCO2Me)(F)]PF6

Abstract  

The reactivity of the trinuclear palladium cluster [Pd₃(dppm)₃(CO)] ⁿ⁺ (dppm = bis(diphenylphosphinomethane); n = 2, 1) towards F⁻ was investigated by electrochemical and spectroscopic methods. The reaction depends on the charge of the cluster. The chemical reduction of the cluster dication is observed in the presence of F⁻ generating the paramagnetic monocationic cluster. Spin-trapping experiments with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) provided evidence for the radical F^• as an intermediate. In a similar manner to the dication, the monocationic cluster [Pd₃(dppm)₃(CO)]⁺ is also reduced, but in a slower process, by the F⁻ ion to produce [Pd₃(dppm)₃(CO)]⁰. Additionally, the alkyne cluster adducts [Pd₃(dppm)₃(CO)(RCCR)] ⁿ⁺ (n = 2, 1; R = CO₂Me) are also reactive towards F⁻. Particularly, the dication adduct leads to a metastable fluoride adduct [Pd₃(dppm)₃(CO)(RCCR)(F)]⁺. The electroreductive behavior of this adduct involves electron-transfer steps and F⁻ exchange equilibriums, for which digital simulation enables the extraction of the thermodynamic parameters (standard potentials and equilibrium constants). Concurrently, the monocation adduct [Pd₃(dppm)₃(CO)(RCCR)]⁺ with F⁻, leads to a disproponation generating 0.5 equiv. of [Pd₃(dppm)₃(CO)(RCCR)(F)]⁺ and 0.5 equiv. of [Pd₃(dppm)₃(CO)(RCCR)]⁰. The former slowly evolves to [Pd₃(dppm)₃(RCCR)(F)]⁺, which was described by X-ray diffraction method.     

Laser desorption/ionization fourier transform mass spectrometry of thin films deposited on silicon by plasma polymerization of acetylene

Thin films deposited on silicon substrate by three different methods of plasma polymerization of acetylene were analyzed by direct laser desorption/ionization Fourier transform mass spectrometry. High-resolution mass spectra showed the presence of carbon clusters and hydrocarbon oligomers in different relative abundances. During unipolar and continuous discharge polymerization of acetylene-hydrogen gas mixtures, quadrupole mass spectra of the plasma constituents showed the presence of molecular species with m/z lower than 100 — mainly peaks of C₄H₂ and C₆H₂. Films produced had smooth surfaces and the corresponding LDI-FTMS spectra displayed only carbon cluster signals in the positive ion mode and both hydrocarbon and carbon cluster signals (with much higher relative abundance of carbon cluster signals) in the negative ion mode. Alternatively, during bipolar discharge with either higher acetylene gas flux (>40 cm³/min) or longer deposition times (>10 min), quadrupole mass spectra of the plasma constituents showed signals corresponding to polycyclic aromatic hydrocarbons (PAH) with m/z higher than 100. SEM pictures of the bipolar thin films demonstrated the presence of “flower” structures and nanoparticles developed on the surface. LDI-FTMS spectra of such thin films showed either total absence or lower relative abundance of carbon cluster signals, compared with hydrocarbon signals.     

Theoretical Characterization of Charge Transport in One‐Dimensional Collinear Arrays of Organic Conjugated Molecules

A great deal of interest has recently focused on host–guest systems consisting of one‐dimensional collinear arrays of conjugated molecules encapsulated in the channels of organic or inorganic matrices. Such architectures allow for controlled charge and energy migration processes between the interacting guest molecules and are thus attractive in the field of organic electronics. In this context, we characterize here at a quantum‐chemical level the molecular parameters governing charge transport in the hopping regime in 1D arrays built with different types of molecules. We investigate the influence of several parameters (such as the symmetry of the molecule, the presence of terminal substituents, and the molecular size) and define on that basis the molecular features required to maximize the charge carrier mobility within the channels. In particular, we demonstrate that a strong localization of the molecular orbitals in push–pull compounds is generally detrimental to the charge transport properties.     

Default policies for global optimisation of noisy functions with severe noise

Global optimisation of unknown noisy functions is a daunting task that appears in domains ranging from games to control problems to meta-parameter optimisation for machine learning. We show how to incorporate heuristics to Stochastic Simultaneous Optimistic Optimization (STOSOO), a global optimisation algorithm that has very weak requirements from the function. In our case, heuristics come in the form of Covariance Matrix Adaptation Evolution Strategy (CMA-ES). The new algorithm, termed Guided STOSOO (STOSOO-G), combines the ability of CMA-ES for fast local convergence (due to the algorithm following the “natural” gradient) and the global optimisation abilities of STOSOO. We compare all three algorithms in the “harder” parts of the Comparing Continuous Optimisers on Black-Box Optimization Benchmarking benchmark suite, which provides a default set of functions for testing. We show that our approach keeps the best of both worlds, i.e. the almost optimal exploration/exploitation of STOSOO with the local optimisation strength of CMA-ES.     

A brief overview of space applications for ultrasonics

Sonics and space are two topics which are not commonly considered together. However, sonic and ultrasonic models, devices and systems have space applications in both science and engineering, as well as showing promise in fields such as cleaning, healthcare and construction. This short paper describes some of these activities and appears as results start to come in from the Curiosity rover, which landed on Mars on the 6th of August, 2012, with over 20 piezoelectric and mechanically-resonant components on board.     

Magnetic properties of bio-synthesized zinc ferrite nanoparticles

The magnetic properties of zinc ferrite (Zn-substituted magnetite, Zn_yFe_1-yFe₂O₄) formed by a microbial process compared favorably with chemically synthesized materials. A metal reducing bacterium, Thermoanaerobacter, strain TOR-39 was incubated with Zn_xFe_1−xOOH (x=0.01, 0.1, and 0.15) precursors and produced nanoparticulate zinc ferrites. Composition and crystalline structure of the resulting zinc ferrites were verified using X-ray fluorescence, X-ray diffraction, transmission electron microscopy, and neutron diffraction. The average composition from triplicates gave a value for y of 0.02, 0.23, and 0.30 with the greatest standard deviation of 0.02. Average crystallite sizes were determined to be 67, 49, and 25 nm, respectively. While crystallite size decreased with more Zn substitution, the lattice parameter and the unit cell volume showed a gradual increase in agreement with previous literature values. The magnetic properties were characterized using a superconducting quantum interference device magnetometer and were compared with values for the saturation magnetization (M_s) reported in the literature. The averaged M_s values for the triplicates with the largest amount of zinc (y=0.30) gave values of 100.1, 96.5, and 69.7 emu/g at temperatures of 5, 80, and 300 K, respectively indicating increased magnetic properties of the bacterially synthesized zinc ferrites.