Singular finite elements for the sudden-expansion and the die-swell problems

The singular finite element method is used to solve the sudden-expansion and the die-swell problems in order to improve the accuracy of the solution in the vicinity of the singularity and to speed up the convergence. The method requires minor modifications to standard finite element schemes, and even coarse meshes give more accurate results than refined ordinary finite element meshes. Improved normal stress results for the sudden-expansion problem have been obtained for various Reynolds numbers up to 100 using the singular elements constructed for the creeping flow problem. In addition, the normal stresses at the walls appear to be insensitive to the singularity powers used in the construction of the singular basis functions. The die-swell problem is solved using the singular elements constructed for the stick–slip problem. The singular elements accelerate the convergence of the free surface dramatically.     

Beam-helicity asymmetry in photon and pion electroproduction in the Δ(1232)-resonance region at Q2 = 0.35(GeV/c)2

The beam-helicity asymmetry has been measured simultaneously for the reactions p→epγ and p→epπ ⁰ in the Δ(1232)-resonance region at Q ² = 0.35(GeV/c)². The experiment was performed at MAMI with a longitudinally polarized beam and an out-of-plane detection of the proton. The results are compared with calculations based on dispersion relations for virtual Compton scattering and with the MAID model for pion electroproduction. There is an overall good agreement between experiment and theoretical calculations. The remaining discrepancies may be ascribed to an imperfect parametrization of some γ ^(*) N→πN multipoles, mainly contributing to the non-resonant background. The beam-helicity asymmetry in both channels (γ and π ⁰) shows a good sensitivity to these multipoles and should allow future improvement in their parametrization.     

Stress redistribution in notched specimens during fatigue cycling

Most materials exhibit a change in stress-strain relationship when subjected to fatigue stresses. In this work, the effect of this change on the stress distribution across the throat of notched-plate specimens of mild steel is examined. Using a set of strain gages, the strain distribution across the specimens was determined under dynamic conditions for various numbers of cycles. Tests of unnotched specimens were used to obtain the cyclic stress-strain properties for corresponding numbers of cycles, and from these data the stress distribution in the notched specimens was determined. Tests in which the strain amplitude at the notch root was held constant revealed a decreasing maximum stress with fatigue cycles. In another series of tests, in which the load amplitude was constant, the maximum stress amplitude was observed to decrease with number of fatigue cycles, despite an increasing strain amplitude. In both types of tests, the stress-concentration factor was observed to decrease with increasing number of fatigue cycles.     

Preparation of a Series of 5-Methyl-3-(substituted)-[1,2,4]triazines

Procedures for the synthesis of thirty-six 5-methyl-3-(substituted)-[1,2,4]triazines have been described. These compounds were evaluated for antagonism at metabotropic glutamate receptor subtype 5 (mGluR5). Two compounds, 5b and 3c, were determined to be low micromolar inhibitors of mGluR5.     

Measurement of heterogeneous reaction rates: three strategies for controlling mass transport and their application to indium-mediated allylations

We describe three new strategies for determining heterogeneous reaction rates using photomicroscopy to measure the rate of retreat of metal surfaces: (i) spheres in a stirred solution, (ii) microscopic powder in an unstirred solution, and (iii) spheres on a rotating shaft. The strategies are applied to indium-mediated allylation (IMA), which is a powerful tool for synthetic chemists because of its stereoselectivity, broad applicability, and high yields. The rate-limiting step of IMA, reaction of allyl halides at indium metal surfaces, is shown to be fast, with a minimum value of the heterogeneous rate constant of 1 × 10(-2) cm/s, an order of magnitude faster than the previously determined minimum value. The strategies described here can be applied to any reaction in which the surface is retreating or advancing, thereby broadening the applicability of photomicroscopy to measuring heterogeneous reaction kinetics.     

A neutral redox-switchable [2]rotaxane

A limited range of redox-active, rotaxane-based, molecular switches exist, despite numerous potential applications for them as components of nanoscale devices. We have designed and synthesised a neutral, redox-active [2]rotaxane, which incorporates an electron-deficient pyromellitic diimide (PmI)-containing ring encircling two electron-rich recognition sites in the form of dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units positioned along the rod section of its dumbbell component. Molecular modeling using MacroModel guided the design of the mechanically interlocked molecular switch. The binding affinities in CH(2)Cl(2) at 298 K between the free ring and two electron-rich guests--one (K(a) = 5.8 × 10(2) M(-1)) containing a DNP unit and the other (K(a) = 6.3 × 10(3) M(-1)) containing a TTF unit--are strong: the one order of magnitude difference in their affinities favouring the TTF unit suggested to us the feasibility of integrating these three building blocks into a bistable [2]rotaxane switch. The [2]rotaxane was obtained in 34% yield by relying on neutral donor-acceptor templation and a double copper-catalysed azide-alkyne cycloaddition (CuAAC). Cyclic voltammetry (CV) and spectroelectrochemistry (SEC) were employed to stimulate and observe switching by this neutral bistable rotaxane in solution at 298 K, while (1)H NMR spectroscopy was enlisted to investigate switching upon chemical oxidation. The neutral [2]rotaxane is a chemically robust and functional switch with potential for applications in device settings.     

Multiplex digital PCR: breaking the one target per color barrier of quantitative PCR

Quantitative polymerase chain reactions (qPCR) based on real-time PCR constitute a powerful and sensitive method for the analysis of nucleic acids. However, in qPCR, the ability to multiplex targets using differently colored fluorescent probes is typically limited to 4-fold by the spectral overlap of the fluorophores. Furthermore, multiplexing qPCR assays requires expensive instrumentation and most often lengthy assay development cycles. Digital PCR (dPCR), which is based on the amplification of single target DNA molecules in many separate reactions, is an attractive alternative to qPCR. Here we report a novel and easy method for multiplexing dPCR in picolitre droplets within emulsions-generated and read out in microfluidic devices-that takes advantage of both the very high numbers of reactions possible within emulsions (>10(6)) as well as the high likelihood that the amplification of only a single target DNA molecule will initiate within each droplet. By varying the concentration of different fluorogenic probes of the same color, it is possible to identify the different probes on the basis of fluorescence intensity. Adding multiple colors increases the number of possible reactions geometrically, rather than linearly as with qPCR. Accurate and precise copy numbers of up to sixteen per cell were measured using a model system. A 5-plex assay for spinal muscular atrophy was demonstrated with just two fluorophores to simultaneously measure the copy number of two genes (SMN1 and SMN2) and to genotype a single nucleotide polymorphism (c.815A>G, SMN1). Results of a pilot study with SMA patients are presented.     

Precision of Hole-Drilling Residual Stress Depth Profile Measurements and an Updated Uncertainty Estimator

Background

Measurement precision and uncertainty estimation are important factors for all residual stress measurement techniques. The values of these quantities can help to determine whether a particular measurement technique would be viable option.

Objective

This paper determines the precision of hole-drilling residual stress measurement using repeatability studies and develops an updated uncertainty estimator.

Methods

Two repeatability studies were performed on test specimens extracted from aluminum and titanium shot peened plates. Each repeatability study included 12 hole-drilling measurements performed using a bespoke automated milling machine. Repeatability standard deviations were determined for each population. The repeatability studies were replicated using a commercially available manual hole-drilling milling machine (RS-200, Micro-Measurements). An updated uncertainty estimator was developed and was assessed using an acceptance criterion. The acceptance criterion compared an expected percentage of points (68%) to the fraction of points in the stress versus depth profile where the measured stresses ± its total uncertainty contained the mean stress of the repeatability studies.

Results

Both repeatability studies showed larger repeatability standard deviations at the surface that decay quickly (over about 0.3 mm). The repeatability standard deviation was significantly smaller in the aluminum plate (max ≈ 15 MPa, RMS?≈?6.4 MPa) than in the titanium plate (max ≈ 60 MPa, RMS?≈?21.0 MPa). The repeatability standard deviations were significantly larger when using the manual milling machine in the aluminum plate (RMS?≈?21.7 MPa), and for the titanium plate (RMS?≈?18.9 MPa).

Conclusions

The single measurement uncertainty estimate met a defined acceptance criterion based on the confidence interval of the uncertainty estimate.

     

Structural study of the Diels-Alder reaction between tetrachlorodimethoxycyclopentadiene and the nickelocene-dimethyl acetylenedicarboxylate adduct. Crystal structures of the products

The cyclopentadienylnickel complex (2) and the parent dimethyl norbornadienedicarboxylate (4) each react with 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene (3) on the less hindred exo-face of the dienophile to produce anti-sequinorbornane adducts 5 and 6. X-ray crystal structures of these adducts have been determined and refined to R values of 0.029 and 0.042 respectively.