Modal stability of inclined cables subjected to vertical support excitation

In this paper the out-of-plane dynamic stability of inclined cables subjected to in-plane vertical support excitation is investigated. We compute stability boundaries for the out-of-plane modes using rescaling and averaging methods. Our study focuses on the 2:1 internal resonance phenomenon between modes that occurs when the excitation frequency is twice the first out-of-plane natural frequency of the cable. The second in-plane mode is excited directly, while the out-of-plane modes can be excited parametrically. An analytical model is developed in order to study the stability regions in parameter space. In this model we include nonlinear coupling effects with other modes, which have thus far been omitted from previous models of parametric excitation of inclined cables. Our study reflects the importance of such effects. Unstable parameter regions are defined for the selected cable configuration. The validity of the proposed stability model was tested experimentally using a small-scale cable actuator rig. A comparison between experimental and analytical results is presented in which very good agreement with model predictions was obtained.     

On optical depth profiling using confocal Raman spectroscopy

Until 2006 the performance of confocal Raman spectroscopy depth profiling was typically described and modeled through the application of geometrical optics, including refraction at the surface, to explain the degree of resolution and the precise form of the depth profile obtained from transparent and semicrystalline materials. Consequently a range of techniques, physical and analytical, was suggested to avoid the errors thus encountered in order to improve the practice of Raman spectroscopy, if not the understanding of the underlying mechanisms. These approaches were completely unsuccessful in accounting for the precise form of the depth profile, the fact that spectra obtained from laminated samples always contain characteristic peaks from all materials present both well above and below the focal point and that spectra can be obtained when focused some 40 μm above the sample surface. This paper provides further evidence that the physical processes underlying Raman spectroscopy are better modeled and explained through the concept of an extended illuminated volume contributing to the final Raman spectrum and modeled through a photon scattering approach rather than a point focus ray optics approach. The power of this numerical model lies in its ability to incorporate, simultaneously, the effects of degree of refraction at the surface (whether using a dry or oil objective lens), the degree of attenuation due to scatter by the bulk of the material, the Raman scattering efficiency of the material, and surface roughness effects. Through this we are now able to explain why even removing surface aberration and refraction effects through the use of oil immersion objective lenses cannot reliably ensure that the material sampled is only that at or close to the point of focus of the laser. Furthermore we show that the precise form of the depth profile is affected by the degree of flatness of the surface of the sample. Perhaps surprisingly, we show that the degree of flatness of the material surface is, in fact, more important than obtaining a precise refractive index match between the immersion oil and the material when seeking a high-quality depth profile or Raman spectrum from within a transparent or semicrystalline material, contrary to accepted norms that samples for interrogation by Raman spectroscopy require little preparation.     

Tricyclic-isoxazolidine analogues via intramolecular 1,3-dipolar cycloaddition reactions of nitrones

The tricyclic-isoxazolidine analogues tetrahydrothiochromenoisoxazoles, hexahydroisoxazolequinolines and tetrahydroisoxazolepyranopyridines were prepared by an intramolecular 1,3-dipolar cycloaddition reaction of a nitrone with an alkene. For N-alkylated hexahydroisoxazolequinolines, reduction of the reaction time from two days to 40 min was achieved using microwave heating. The cyclization to form tetrahydroisoxazolepyranopyridines only proceeded when the alkene was substituted with an electron withdrawing group.     

Determination of optical properties of slices of turbid media by diffuse CW laser light scattering profilometry

In this work we present a method for determining the optical parameters of turbid media, namely its absorption coefficient (μ_a) and its reduced scattering coefficient . It is based on the measurement of CW transmittance profiles and analysis of the experimental data by a theoretical model based on the diffusion approximation (DA) of the radiative transfer equation (RTE). The method developed has been investigated with solid polymer probes but it could be applied for liquid materials as well. Experimental results are presented and compared to those of other authors together with a discussion about the accuracy of measurements. In addition, measurements using integrating spheres as well as Monte Carlo simulations are also presented to validate these results.     

“Crowned” Univalent Indium Complexes as Donors? Experimental and Computational Insights on the Valence Isomers of EE′X4 Species

The use of the univalent indium reagent [In([18]crown-6)][OTf] as a donor is investigated by its reactions with acceptors including InX(3) (X=Cl, Br, I). The donor-acceptor complexes of the form [X([18]crown-6)In-InX(3)] obtained in this manner represent the first new isomeric form of indium(II) halides identified for at least five decades. The formation of such complexes appears to be particularly favorable and they are isolated as products in many reactions involving low-valent indium, a halide source, and [18]crown-6. A convenient solution-phase synthesis of In[ECl(4)] salts is reported. This facile and direct syntheses of In[ECl(4)] (E=Al, Ga, In) salts allows for the in situ preparation and isolation of crown-ether complexes of the form [In([18]crown-6)][ECl(4)], whose existence had been postulated but never confirmed. Solution-phase and solid-state NMR experiments reveal that these compounds can exist as either donor-acceptor complexes or ionic salts, depending on the phase of the system, the nature of the solvent employed, and the identity of the metalate anion involved. Similar investigations into the effect of a smaller crown ether allow for the isolations of salts containing the cation [In([15]crown-5)](+). Computational investigations into the nature of the crowned univalent indium donor fragments, and on the donor-acceptor complexes produced, demonstrate the influence of anionic substituents on the reactivity of lone pair of electrons of the In(I) center. Natural bond orbital (NBO) analysis of donor-acceptor models shows that the composition of the E-E bond MO should provide the ability to predict which models should form stable complexes.     

From sulfur-amine solutions to metal sulfide nanocrystals: peering into the oleylamine-sulfur black box

In this Article, we present our findings on the formation of metal sulfide nanocrystals from sulfur-alkylamine solutions. By pulsed field gradient diffusion NMR along with the standard toolbox of 1D and 2D NMR, we determined that sulfur-amine solutions used as a sulfur precursor exist as alkylammonium polysulfides at low temperatures. Upon heating to temperatures used in nanocrystal synthesis, the polysulfide ions react with excess amine to generate H(2)S, which combines with the metal precursor to form metal sulfide. Four different reaction pathways were found, each of which produced H(2)S and the byproducts identified in this Article. Thioamides were identified as an intermediate and were shown to exhibit much more rapid kinetics than sulfur-alkylamine solutions at low temperatures in the synthesis of metal sulfide nanocrystals.     

Resolution of conflicting views concerning frequency-response models for conducting materials with dispersive relaxation, and isomorphism of macroscopic and microscopic models

Possible errors in the widely used 1972–1973 macroscopic original-electric-modulus formalism are identified, corrected, and their consequences considered. These errors include misidentification of the high-frequency-limiting dielectric constant arising entirely from mobile charges, ε_C1∞, and the failure to treat properly the high-frequency-limiting dielectric constant associated with bulk dipolar and vibrionic effects, ε_D∞. It is shown that the corrected modulus formalism, which describes dispersed mobile-charge effects, is isomorphic in form with the 1973 microscopic continuous-time random-walk hopping model of Scher and Lax after a minor but significant correction is made to the latter's response function. This firmly established correction, which nevertheless could not be determined by Kronig–Kramers transformation, involved inversion of synthetic frequency-response data to determine a distribution of relaxation times and led to extension of the real part of the Scher–Lax dielectric response to higher frequencies by the inclusion of a nonzero limiting value. This isomorphism, along with excellent data fitting using the corrected modulus formalism, suggests that since the Scher–Lax stochastic model involves no explicit Coulomb interactions, cation motion in glasses is dominated by short-range interactions. Finally, two very-high-frequency processes, which each lead to a limiting plateau value of the real part of the conductivity at sufficiently high frequencies, are discussed in detail.     

On the Marzke-Wheeler and Desloge constructions

There is no indication of time dilation of clocks or of length contraction of rods in Marzke and Wheeler's clock or in Desloge's metrosphere.