Structure of 1-(1-adamantyl)pyrazoles : Crystal geometry and carbon-13 nmr spectroscopy

Crystal structures of 1-(1-adamantyl)pyrazole, 1a, and 1-(1-adamantyl-3-ol)-4-nitropyrazole, 2a, have been solved by X-ray analysis. The space groups and cell parameters are P2₁, a, 7.4021(3), b, 10.7529(5),c, 6.9651(2)Å, β, 90.206(3)° for 1a with Z = 2 and P2/n, a, 31.1172(14), b, 6.8506(1), c, 12.0313(3)Å, β 94.873(3)° for 2a with Z = 8. Refinements were carried out down to R values of 0.043 (R_w, = 0.046) and 0.079 (R_w = 0.061) for the 951 (2σ(I)) and 2461 (3σ(I)) observed reflections respectively. The conformation about the bond between the heterocycle and the carbocycle is discussed on theoretical grounds INDO calculations): the adamantane behaves as a free rotor. The stcricinteractions of the adamantyl residue with the methyl substituents in 2- and 5-position of pyrazole are apparent in the C-13 chemical shifts.     

Superdiffusion and encounter rates in diluted,low dimensional worlds

Rate limitation due to encounters is fundamental to many ecological interactions. Since encounter rate governs reaction rates, and thus, dynamics of systems, it deserves systematic study. In classical population biology, ecological dynamics rely on the assumption of perfectly mixed interacting entities (e.g., individuals, populations, etc.) in a spaceless world. The so-called mean field assumption assumes that encounter rates are driven exclusively by changes in the density of the interacting entities and not on how they are distributed or move in space. Therefore, the mean field assumption does not give any insight into relevant spatiotemporal statistical properties produced by the trajectories of moving entities through space. In the present study, we develop spatially explicit simulations of random walking particles (i.e., Lévy walkers) to evaluate encounter rate constraints beyond the mean field assumption. We show that encounter rate fluctuations are driven not only by physical aspects such as the size or the velocity of the interacting particles, but also by different motion patterns. In particular, superdiffusion phenomena might be relevant at low densities and/or low spatial dimensionality. Finally, we discuss potential adaptive responses of living organisms that may allow individuals to control how they diffuse through space and/or the spatial dimensions employed in the exploration process.     

On the effects of non-linear elements in the reliability-based optimal design of stochastic dynamical systems

The aim of the present paper is to study the effects of non-linear devices on the reliability-based optimal design of structural systems subject to stochastic excitation. One-dimensional hysteretic devices are used for modelling the non-linear system behavior while non-stationary filtered white noise processes are utilized to represent the stochastic excitation. The reliability-based optimization problem is formulated as the minimization of the expected cost of the structure for a specified failure probability. Failure is assumed to occur when any one of the output states of interest exceeds in magnitude some specified threshold level within a given time duration. Failure probabilities are approximated locally in terms of the design variables during the optimization process in a parallel computing environment. The approximations are based on a local interpolation scheme and on an efficient simulation technique. Specifically, a subset simulation scheme is adopted and integrated into the proposed optimization process. The local approximations are then used to define a series of explicit approximate optimization problems. A sensitivity analysis is performed at the final design in order to evaluate its robustness with respect to design and system parameters. Numerical examples are presented in order to illustrate the effects of hysteretic devices on the design of two structural systems subject to earthquake excitation. The obtained results indicate that the non-linear devices have a significant effect on the reliability and global performance of the structural systems.     

Comparison of various detection limit estimates for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection

This paper addresses the variations that presently exist regarding the definition, determination, and reporting of detection limits for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection (GC-PFPD). Gas standards containing hydrogen sulphide (H(2)S), carbonyl sulphide (COS), sulphur dioxide (SO(2)), methyl mercaptan (CH(3)SH), dimethyl sulphide (DMS), carbon disulphide (CS(2)), and dimethyl disulphide (DMDS) in concentrations varying from 0.36ppb (v/v) up to 1.5ppm (v/v) in nitrogen were prepared with permeation tubes and introduced in the gas chromatograph using a 0.25-ml gas sampling loop. After measuring the PFPD response versus concentration, the method detection limit (MDL), the Hubaux-Vos detection limit (x(D)), the absolute instrument sensitivity (AIS), and the sulphur detectivity (D(s)) were determined for each sulphur compound. The results show that the MDL determined by the US Environmental Protection Agency procedure consistently underestimates the minimum concentrations of volatile sulphur compounds that can be practically distinguished from the background noise with the PFPD. The Hubaux-Vos detection limits and the AIS values are several times higher than the MDL, and provide more conservative estimates of the lowest concentrations that can be reliably detected. Sulphur detectivities are well correlated with AIS values but only poorly correlated with MDL values. The AIS is recommended as a reliable and cost-effective measure of detection limit for volatile sulphur compounds by GC-PFPD, since the AIS is easier and faster to determine than the MDL and the Hubaux-Vos detection limit. In addition, this study confirmed that the PFPD response is nearly quadratic with respect to concentration for all volatile sulphur compounds.     

Elastic and anelastic relaxations in the relaxor ferroelectric Pb(Mg1/3Nb2/3)O3: I. Strain analysis and a static order parameter

The structural evolution of Pb(Mg(1/3)Nb(2/3))O(3) (PMN) has been reviewed in terms of characteristic temperatures, length scales and timescales, with a view to considering the overall relaxor behaviour from the perspectives of strain and elasticity. A conventional analysis of lattice parameter data in terms of spontaneous strain and strain/order parameter coupling shows that even though a normal phase transition does not occur the relaxor ordering process is accompanied by a significant volume strain which follows the pattern of a static order parameter evolving according to that expected for a tricritical phase transition with T(c) ≈ 350 K. This matches the evolution of the intensity of the elastic central peak in neutron scattering spectra, and reflects the development of static (or quasistatic) polar nanoregions (PNRs) as if by a mean-field phase transition. Use of a Landau free energy expansion, which includes Γ4(-) order parameter components to describe ferroelectric contributions and an R1(+) order parameter to describe cation ordering together with their formal coupling with strain, then allows the pattern of elastic softening expected for a cubic → rhombohedral phase transition to be anticipated. The extent to which observed softening differs from this static mean-field pattern serves to highlight the additional roles of local heterogeneity and relaxation dynamics in determining the relaxor properties of PMN.     

Synthesis and biological evaluation of new bicyclic fluorinated uracils through ring-closing metathesis

Two families of bicyclic fluorinated uracils have been prepared starting from a gem-difluorinated unsaturated nitrile, by means of a ring-closing metathesis reaction to form the new ring, which is fused at the C-5/C-6 or N-1/C-6 positions of the uracil moiety. The selective formation of olefin regioisomers in the metathesis process can be controlled according to the reaction conditions (catalyst, solvent, and temperature). The acaricidal activities of the resulting compounds have also been investigated.     

Solid-phase selenium-catalyzed selective allylic chlorination of polyprenoids: facile syntheses of biologically active terpenoids

Regioselective halogenation of the terminal isopropylidene unit of different acyclic polyolefinic polyprenoids (farnesyl acetate, geranylgeranyl acetate, squalene, etc.) using NCS/catalytic polymer-supported selenenyl bromide is described; good to excellent yields are obtained (68-96%). The first applications of this protocol include the concise synthesis of bioactive terpenoids 1-3.     

Polar domains in lead titanate films under tensile strain

Thin films of PbTiO3, a classical ferroelectric, have been grown under tensile strain on single-crystal substrates of DyScO3. The films, of only 5 nm thickness, grow fully coherent with the substrate, as evidenced by synchrotron x-ray diffraction. A mapping of the reciprocal space reveals intensity modulations (satellites) due to regularly spaced polar domains in which the polarization appears rotated away from the substrate normal, characterizing a low-symmetry phase not observed in the bulk material. This could have important practical implications since these phases are known to be responsible for ultrahigh piezoelectric responses in complex systems.