Theory and model implementation for analyzing line structures subject to dynamic motions of large deformation and elongation using the absolute nodal coordinate formulation (ANCF) approach

This paper presents the theory development and numerical implementation of a new gradient-deficient-based ANCF (Absolute Nodal Coordinate Formulation) model applied to perform the nonlinear dynamic analysis of elastic line structures subject to large stretching and deformation. The derivations of model equations, introduced numerical approaches, and result validations are the focuses of this study. Different from the traditional rod theory for small stretching consideration, the present model implements the line structures’ large elongation concepts into both the control mechanisms of constitutive formulations and equations of motion. The effect of external hydrodynamic forces on structures is also included in the model formulations. Based on the conservation of energy, the line model developed in this study covers the variation in strain and takes a full account of the bending effect with large stretching. A finite-element-based implicit scheme according to a modified Newmark-beta method is employed to solve the assembled system equations with unknown variables of nodal position vectors, their tangential derivatives, and strains. Selected cases with dynamic motions, such as nonlinear oscillation of a compound pendulum, free falling of a horizontal elastic beam in air with two different settings of gravity, free falling of a submerged horizontal tether with and without an attached concentrated mass, and a submerged vertical tether with a prescribed translational motion, are simulated to verify the developed model by comparing the results with analytical solutions and published experimental data and numerical results. It is found the present ANCF model, as noticed with good matched results with analytical solutions, measurements and other published solutions, is demonstrated to be able to provide converged and reasonably accurate predictions on the responses of line structures subject to large dynamic motions.

     

NMR studies on 4‐thio‐5‐furan‐modified and 4‐thio‐5‐thiophene‐modified nucleosides

Systematic NMR characterization of 4‐thio‐5‐furan‐pyrimidine nucleosides or 4‐thio‐5‐thiophene‐pyrimidine nucleosides (ribonucleosides and 2′‐deoxynucleosides) was performed. All proton and carbon signals of 4‐thio‐5‐thiophene‐ribouridine and related analogues were unambiguously assigned. The orientations of the base (4‐thiouridine or its deoxy analogue) relative to the ring (furan or thiophene) are explored by a NMR approach and further supported by X‐ray crystallographic studies. The procedures presented here would be applicable to other modified nucleosides and nucleotides. Copyright © 2016 John Wiley & Sons, Ltd.     

Metal complexes as potential modulators of inflammatory and autoimmune responses

Over the past few decades, the realm of inorganic medicinal chemistry has been dominated by the study of the anti-cancer properties of transition metal complexes, particularly those based on platinum or ruthenium. However, comparatively less attention has been focused on the development of metal complexes for the treatment of inflammatory or autoimmune diseases. Metal complexes possess a number of advantages that render them as attractive alternatives to organic small molecules for the development of therapeutic agents. In this perspective, we highlight recent examples in the development of transition metal complexes as modulators of inflammatory and autoimmune responses. The studies presented here serve to highlight the potential of transition metal complexes in modulating inflammatory or immune pathways in cells.     

Palladium‐Catalyzed Direct Cross‐Coupling of Carboranyllithium with (Hetero)Aryl Halides

A palladium‐catalyzed direct C‐arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides.     

α‐Diamine Nickel Catalysts with Nonplanar Chelate Rings for Ethylene Polymerization

A series of novel α‐diamine nickel complexes, (ArNH‐C(Me)‐(Me)C‐NHAr)NiBr₂, 1 : Ar=2,6‐diisopropylphenyl, 2 : Ar=2,6‐dimethylphenyl, 3 : Ar=phenyl), have been synthesized and characterized. X‐ray crystallographic analysis showed that the coordination geometry of the α‐diamine nickel complexes is markedly different from conventional α‐diimine nickel complexes, and that the chelate ring (N‐C‐C‐N‐Ni) of the α‐diamine nickel complex is significantly distorted. The α‐diamine nickel catalysts also display different steric effects on ethylene polymerization in comparison to the α‐diimine nickel catalyst. Increasing the steric hindrance of the α‐diamine ligand by substitution of the o‐methyl groups with o‐isopropyl groups leads to decreased polymerization activity and molecular weight; however, catalyst thermal stability is significantly enhanced. Living polymerizations of ethylene can be successfully achieved using 1 /Et₂AlCl at 35 °C or 2 /Et₂AlCl at 0 °C. The bulky α‐diamine nickel catalyst 1 with isopropyl substituents can additionally be used to control the branching topology of the obtained polyethylene at the same level of branching density by tuning the reaction temperature and ethylene pressure.     

Creating Coordination‐Based Cavities in a Multiresponsive Supramolecular Gel

Creating cavities in varying levels, from molecular containers to macroscopic materials of porosity, have long been motivated for biomimetic or practical applications. Herein, we report an assembly approach to multiresponsive supramolecular gels by integrating photochromic metal–organic cages as predefined building units into the supramolecular gel skeleton, providing a new approach to create cavities in gels. Formation of discrete O‐Pd₂L₄ cages is driven by coordination between Pd²⁺ and a photochromic dithienylethene bispyridine ligand (O‐PyFDTE). In the presence of suitable solvents (DMSO or MeCN/DMSO), the O‐Pd₂L₄ cage molecules aggregate to form nanoparticles, which are further interconnected through supramolecular interactions to form a three‐dimensional (3D) gel matrix to trap a large amount of solvent molecules. Light‐induced phase and structural transformations readily occur owing to the reversible photochromic open‐ring/closed‐ring isomeric conversion of the cage units upon UV/visible light radiation. Furthermore, such Pd₂L₄ cage‐based gels show multiple reversible gel–solution transitions when thermal‐, photo‐, or mechanical stimuli are applied. Such supramolecular gels consisting of porous molecules may be developed as a new type of porous materials with different features from porous solids.