Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes - Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλ_abs up to 25 nm) and emissions (Δλ_em up to 73 nm, Φ_PL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in ¹H NMR spectroscopy (218 K), N−CH₂ protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol⁻¹. This phenomenon is due to planar chiral conformations (S_p and R_p configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.     

Experimental investigation of the failure mechanism of fiber-reinforced composites subjected to uniaxial tension

In this investigation, the components of displacement in the axial direction throughout the surface of a unilayer, fiber-reinforced-composite tension specimen subjected to low-speed loading are established experimentally. The experimental results are used to evaluate the strain distribution throughout the surface of the specimen; to establish the strain concentration at the surface in the neighborhood of broken fibers; and to evaluate other factors.     

Plane steady vibration of an elastic wedge

The problem of plane steady vibration of an elastic wedge of arbitrary angle (less than 180 degrees) subject to harmonic normal and shearing tractions on its faces is reduced to a system of singular integral equations by the superposition of two half-plane solutions. The integral equations have kernels with Cauchy singularities of a non-translation type, except for the 90 degree wedge. The locations of these singularity lines are shown graphically as a function of wedge angle.     

Bond stresses for a composite material reinforced with various arrays of fibers

The problem treated here is that of an isotropic body having a doubly periodic rectangular or triangular array of perfectly bonded circular elastic inclusions. The body is in tension or compression. This simulates a composite material wherein a relatively weak matrix is reinforced by stronger (and more rigid) fibers. Bond stresses for both rectangular and triangular arrays have been calculated using either boundary point matching or boundary point least squares techniques. Numerical results based on a plane strain analysis are given in graphical form.     

Ten-deg off-axis test for shear properties in fiber composites

A combined theoretical and experimental investigation was conducted to assess the suitability of the 10-deg off-axis tensile-test specimen for the intralaminar-shear characterization of unidirectional composites. Composite mechanics, a combined-stress failure criterion and a finiteelement analysis were used to determine theoretically the stress-strain variation across the specimen width and the relative stress and strain magnitudes at the 10-deg plane. Strain gages were used to measure the strain variation across the specimen width at specimen midlength and near the end tabs. Specimens from Mod-I/epoxy. T-300/epoxy, and S-glass/epoxy were used in the experimental program. It was found that the 10-deg off-axis tensile-test specimen is suitable for intralaminar-shear characterization and it, is recommended that it should be considered as a possible standard test specimen for such a characterization.     

An analysis on effect of transverse convex curvature on turbulent flow and heat transfer

An analysis based on a model of modified mixing length by Hornby, Mistry und Barrow [1] was made on the effect of transverse convex curvature in turbulent boundary layer for incompressible axial flows along circular cylinders. The deviation of various turbulent flow and heat transfer properties from those of flat plates is presented. The agreement between the analyses and the experimental results for skin friction and heat transfer rate is good. The study demonstrated that, for a given condition, both the friction coefficient and Stanton number increase with decreasing value of the cyclinder radius and that their values are always greater than those for the flow over a flat plate.     

Throughput and coupling in optical fibers

Optical throughput, namely the product of area times subtending solid, is a useful concept in calculations of light coupling to optical fibers. It is invariant through an optical system, thus providing a simple and elegant way to derive the maximum coupling efficiency between a light source and a fiber, regardless of intervening optics. Because throughput is proportional to the number of modes supported by an optical structure, it also yields the distribution of modal power within a fiber.In this paper, we illustrate applications of throughput by calculating light coupling into fibers and mode distribution within.     

A machine for static and dynamic triaxial testing

A machine has been developed for studying the static and dynamic triaxial constitutive behavior of large specimens of geologic and construction materials. Test specimens can also contain a cylindrical tunnel cavity to permit study of tunnel-reinforcement structures and rock-structure interaction. The specimens are 0.3 m in diameter and 0.3 to 0.45 m high; the model tunnels can be up to 50 mm in diameter. Static and dynamic triaxial loads can be applied with maximum pressures of 200 MPa in static tests and 100 MPa in dynamic tests. Dynamic loading can also be superimposed on a static preload as large as 20 MPa. To facilitate study of tunnel reinforcement, the tunnel is maintained at ambient pressure, with access at both ends for instrumentation and photography. Example results show the influence on tunnel deformation of loading rate as well as the presence of joints and their orientation. For a given allowable tunnel closure, substantially greater pressures can be sustained under dynamic loading than under static loading, and substantially greater pressures can be sustained by an intact specimen than by a jointed specimen.     

Energy release rates in a constrained epoxy disc with Hookean and Mooney–Rivlin materials

Assuming that the disc material can be modeled either as Mooney–Rivlin or as Hookean and the steel ring enclosing the disc as Hookean, the energy release rates as a function of the crack length are evaluated and compared. Two loadings are considered––one in which the surface of the star shape hole in the disc is loaded by a uniform pressure and the other in which the temperature of the composite body is uniformly raised. It is found that the linear and the nonlinear analyses give qualitatively similar results for the two loadings. For each load, the energy release rate increases with an increase in the starter crack length, reaches a maximum value and then decreases gradually.