Slip, stick, and reverse slip characteristics during dynamic fibre pullout

Inertial effects in the mechanism of fibre pullout (or push-in) are examined, with emphasis on how the rate of propagation of stress waves along the fibre, and thence the pullout dynamics, are governed by friction and the propagation of companion waves excited in the matrix. With a simple shear lag model (assuming zero debond energy at the fibre/matrix interface), the effect of uniform frictional coupling between the fibre and the matrix is accounted for in a straightforward way. Analytical solutions are derived when the pullout load increases linearly in time. The process zone of activated material is generally divided into two or three domains along the axis of the fibre. Within these domains, slip in the sense implied by the load, slip in the opposite sense (reverse slip), and stick may be observed. The attainable combinations define three regimes of behavior, which are realized for different material parameter values. The elastodynamic problem is also solved more accurately using a plane stress finite element method, with friction represented by an interfacial cohesive zone. The predictions of the shear lag theory are broadly confirmed.     

Total Synthesis of (±)-Phyllantidine: Development and Mechanistic Evaluation of a Ring Expansion for Installation of Embedded Nitrogen-Oxygen Bonds

The development of a concise total synthesis of (±)-phyllantidine ( 1 ), a member of the securinega family of alkaloids containing an unusual oxazabicyclo[3.3.1]nonane core, is described. The synthesis employs a unique synthetic strategy featuring the ring expansion of a substituted cyclopentanone to a cyclic hydroxamic acid as a key step that allows facile installation of the embedded nitrogen-oxygen (N−O) bond. The optimization of this sequence to effect the desired regiochemical outcome and its mechanistic underpinnings were assessed both computationally and experimentally. This synthetic approach also features an early-stage diastereoselective aldol reaction to assemble the substituted cyclopentanone, a mild reduction of an amide intermediate without N−O bond cleavage, and the rapid assembly of the butenolide found in ( 1 ) via use of the Bestmann ylide.     

Shaping suvorexant: application of experimental and theoretical methods for driving synthetic designs

Dual Orexin Receptor Antagonists (DORA) bind to both the Orexin 1 and 2 receptors. High resolution crystal structures of the Orexin 1 and 2 receptors, both class A GPCRs, were not available at the time of this study, and thus, ligand-based analyses were invoked and successfully applied to the design of DORAs. Computational analysis, ligand based superposition, unbound small-molecule X-ray crystal structures and NMR analysis were utilized to understand the conformational preferences of key DORAs and excellent agreement between these orthogonal approaches was seen in the majority of compounds examined. The predominantly face-to-face (F2F) interaction observed between the distal aromatic rings was the core 3D shape motif in our design principle and was used in the development of compounds. A notable exception, however, was seen between computation and experiment for suvorexant where the molecule exhibits an extended conformation in the unbound small-molecule X-ray structure. Even taking into account solvation effects explicitly in our calculations, we nevertheless find support that the F2F conformation is the bioactive conformation. Using a dominant states approximation for the partition function, we made a comprehensive assessment of the free energies required to adopt both an extended and a F2F conformation of a number of DORAs. Interestingly, we find that only a F2F conformation is consistent with the activities reported.     

Measurements of the VLBI experiments during the first campaign of the Asian-Pacific space geodynamics (APSG) program

During the first campaign of the Asian-Pacific space geodynamics (APSG) program in October 1997, two VLBl experiments were successfully organized and coordinated by the Astrometry and Geodesy VLBl Group of Shanghai Astronomical Observatory, the Chinese Academy of Sciences, cooperated with geodetic VLBl group, GSFC, NASA, USA. Six VLBl stations participated in the experiments, including Seshan and Urumqi station of China, Gilcreek station in Alaska and Kokee station in Hawaii of USA, Kashima station of Japan and Hobart station at Tasmania of Australia. Baseline lengths are from 1 900 to 11 000 km and the mean relative uncertainty of the baseline length measurements is 1.0 x 10^-9. In addition, the rates of the baseline lengths among the six stations and their three-dimensional velocities are solved out via global analysis of the two APSG sessions and the historical observations of the six stations as well as other VLBl observations from the global observation network. These results are appreciable to the studies of the modern crustal movement in the Asian-Pacific region. Especially,an 8 mm/a eastward motion and a 14 mm/a north by northeast motion are detected respectively for Seshan and Urumqi stations relative to the stable part of the Eurasian plate. The motions directly illustrate the effect of the northward movement of Indian plate on the modern crustal motions of the northwestern and the eastern part of China, which is of important significance to the study of the modern crustal motion of China.     

Synthetic studies toward longeracemine: The intramolecular [4+2] cycloaddition of 3H-pyrroles

Model studies to develop a tetracyclization approach mimicking the proposed biosynthesis of the secodaphnane-type alkaloid longeracemine are described. These studies have culminated in the successful implementation of a 3H-pyrrole [4+2] cycloaddition that delivers a longeracemine-like azabicycle containing three contiguous quaternary stereocenters.     

Foam flow around an obstacle: simulations of obstacle–wall interaction

The flow of a two-dimensional foam around an obstacle provides a benchmark experiment in which to study the transition from discrete to continuous properties of this complex fluid. The interaction between the obstacle and the walls of the channel is simulated using the Surface Evolver. The lift and drag forces on a circular obstacle are measured and the contributions to the total force of the film network and the bubble pressures are assessed. As the distance of the obstacle from the wall decreases, the lift force is found to increase significantly whereas the drag force does not vary greatly.A paper presented at the AERC 2005