Conformational properties of propargyloxy-calix[4]arene tricarboxamides: NMR and DFT studies on the O-through-the-annulus rotation

The size limit of substituents allowing O-through-the-annulus rotation of substituted calix[4]arenes was further extended to the propargyloxy group in 24-propargyloxy-25,26,27-tris(N,N-dimethylcarbamoylmethoxy)-p-tert-butylcalix[4]arene by demonstrating its free but slow motion affording equilibrium between the partial cone and 1,2-alternate conformers. The effect of solvent and upper rim substituents R¹ on the conformational inversion was investigated by means of ¹H NMR. The rotational isomerisation of the parent (R¹ = H) analogue could not unambiguously be detected. The experimental results were supported by comprehensive density functional theory studies.     

Shear modulus determination in model hydrogels by means of elongated magnetic nanoprobes

The mechanical characterization of complex soft matter by quasi-static magnetometry using nanoscopic magnetic probes is demonstrated for model hydrogels doped with two types of elongated magnetic nanoparticles. Chemically crosslinked poly(acrylamide) (PAAm) hydrogels serve as the matrix in which nickel nanorods or weakly magnetized hematite (α-Fe₂O₃) ellipsoids are embedded as local probes. We investigated the swelling behavior of the ferrogels in order to verify that their equilibrium swelling degree in water is not influenced by the probes, shows a good correlation with the Frenkel–Flory–Rehner model. The proposed magnetomechanical method relies on a correlation between the shear modulus of the PAAm hydrogel matrix and the coercive fields of the corresponding isotropic ferrogels. By extending the Stoner–Wohlfarth model for single-domain blocked magnetic particles by a term for particle rotation in an elastic matrix, information on the shear modulus of the matrix can be obtained. Comparison of the results with the expected relation from rubber elasticity theory illustrates both the general potential as well as the limits of the approach. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Structures of Highly Twisted Amides Relevant to Amide N−C Cross‐Coupling: Evidence for Ground‐State Amide Destabilization

Herein, we show that acyclic amides that have recently enabled a series of elusive transition‐metal‐catalyzed N?C activation/cross‐coupling reactions are highly twisted around the N?C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N‐glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α‐carbon atom. The ¹⁵N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground‐state twist as a blueprint for activation of amides toward N?C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non‐planar amide bonds.     

A Simple Synthesis of Stable Phosphorus Ylides from Indole and Some of Its Derivatives

Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of strong NH acids, such as indole and 2-methyl indole, 3-methyl indole, and 5-boromo indole. These stable ylides exist in a solution as a mixture of two geometrical isomers as a result of the restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group.     

Effects of Salt on the Orientational Order in Decylammonium Chloride/Ammonium Chloride/Water Systems

The effect of NH₄Cl on the temperature dependence of deuterium oxide splitting (water order) and proton line width (surfactant order) in decylammonium chloride (DACl), D₂O systems is reported. The molar ratio of DACl to D₂O was held constant at .085 and the molar ratio of NH₄Cl to D₂O was varied from .012 to .029. We find for the above concentration ranges that in the nematic range the relative temperature dependence of the D₂O splitting is little affected by changes on salt concentration. The slopes of the proton line widths as a function of temperature decrease with increasing salt concentration. The results are compared with earlier data on salt effects on order obtained with the disodium cromoglycate system.     

Effect of rotation in magneto-thermoelastic transversely isotropic hollow cylinder with three-phase-lag model

This article deals with the various heat source responses in a transversely isotropic hollow cylinder under the purview of three-phase-lag (TPL) generalized thermoelasticity theory. In presence of magnetic field and due to the rotating behavior of the cylinder, the governing equations are redefined for generalized thermoelasticity with thermal time delay. In order to obtain the stress, displacement and temperature field, the field functions are expressed in terms of modified Bessel functions in Laplace transformed domain. When the outer radius of hollow cylinder tends to infinity, the corresponding results are discussed. Finally an appropriate Laplace transform inversion technique is adopted.     

Advancements in subsea riser analysis using quasi-rotations and the Newton–Raphson method

Beam structures undergoing finite deflections and rotations in space have extensive application in the subsea industry particularly for the analysis of holistic systems with larger numbers of mooring and riser components. In using the finite element analysis approach, there is an increasing requirement for large element sizes which preserve accuracy with regard to the coupling of axial, bending and torsion response.The authors outline a method for improving the current state of practice for the analysis of riser systems. The approach draws on the convected coordinates method, Euler–Bernoulli beam theory, the principle of virtual work and the finite element method. Two quasi-rotation measures are developed including a quasi-material rotation definition for rotational deformation relative to the convected axis of a beam and a quasi-space rotation definition to deal with the path dependent nature of rotations in three dimensions.The novel aspect of this work is to relate the rate of change of the quasi-material rotation vector along the beam axis to a linear transformation of the beam axis rate-of-rotation vector through utilising the convected coordinates axes system. In this way, incremental values of quasi-material rotation are directly linked to incremental values of nodal quasi-space rotation and a global Newton–Raphson solution technique for interconnecting beam elements is straightforward to assemble.Furthermore, this leads to accurate definitions of coupled axial, bending and torque response for beams with significant deflection. The approach has particular advantages in the analysis of subsea riser sections. Also, the accuracy of the solution is preserved for a fewer number of elements compared to alternative solutions for computationally sensitive load cases with highly non-linear loading regimes.     

Integral operators commuting with dilations and rotations in generalized Morrey-type spaces

We find conditions for the boundedness of integral operators $K$ commuting with dilations and rotations in a local generalized Morrey space. We also show that under the same conditions, these operators preserve the subspace of such Morrey space, known as vanishing Morrey space. We also give necessary conditions for the boundedness when the kernel is non-negative. In the case of classical Morrey spaces, the obtained sufficient and necessary conditions coincide with each other. In the one-dimensional case, we also obtain similar results for global Morrey spaces. In the case of radial kernels, we also obtain stronger estimates of $Kf$ via spherical means of $f$. We demonstrate the efficiency of the obtained conditions for a variety of examples such as weighted Hardy operators, weighted Hilbert operator, their multidimensional versions, and others.