Theoretical investigation into the structural, thermochemical, and electronic properties of the decathio[10]circulene

For the first time, a theoretical study has been performed on the prototypical decathio[10]circulene (C(20)S(10)) species, which is an analogue of the novel octathio[8]circulene "Sulflower" molecule (C(16)S(8)). Examinations of the singlet and triplet states of C(20)S(10) were made at the B3LYP/6-311G(d) level. Local minima of C(2) and C(s) symmetry were found for the lowest singlet and triplet states, respectively. The stability of C(20)S(10) was assessed by calculating the ΔH°(f) of C(16)S(8) and C(20)S(10) and the ΔH(o) for their decomposition into C(2)S units. Frontier molecular orbital plots show that structural adjacent steric factors along with the twist and strain orientations of C(20)S(10) do not disturb the aromatic π-delocalizing effects. In fact, C(20)S(10) maintains the same p(z) HOMO character as C(16)S(8). These similarities are further verified by density-of-states characterization. Calculated infrared spectra of C(16)S(8) and C(20)S(10) show broad similarities. Molecular electrostatic potential results reveal that eight of the peripheral sulfur atoms are the most electronegative atoms in the molecule, while the interior ten-membered ring exhibits virtually no electronegativity.     

Anatomy of high-performance 2D similarity calculations

Similarity measures based on the comparison of dense bit vectors of two-dimensional chemical features are a dominant method in chemical informatics. For large-scale problems, including compound selection and machine learning, computing the intersection between two dense bit vectors is the overwhelming bottleneck. We describe efficient implementations of this primitive as well as example applications using features of modern CPUs that allow 20-40× performance increases relative to typical code. Specifically, we describe fast methods for population count on modern x86 processors and cache-efficient matrix traversal and leader clustering algorithms that alleviate memory bandwidth bottlenecks in similarity matrix construction and clustering. The speed of our 2D comparison primitives is within a small factor of that obtained on GPUs and does not require specialized hardware.     

An optrode particle geometry to decrease response time

A hollow 3 μm sensing microcapsule containing chromoionophores within a 100 nm organosilica shell is reported. This shows a response to an ion step two orders of magnitude faster than 'filled' sensing particles of similar diameter. Incorporation of chromoionophores ETH 5294 and ETH 7061 in the capsule shell is shown with a t(90) response <2 s compared with >15 min for filled particles of similar diameters. This ultrafast geometry is also extended to dual ionophore dye incorporation and preliminary exploration of a FRET-based ratiometric method is examined to extend the pH response range, using a single excitation wavelength.     

Dynamic coefficient evaluation for an algebraic subgrid stress model

Static model coefficients for an algebraic subgrid stress (SGS) model are determined using a dynamic approach, based on results from simulations of isotropic decaying turbulence. The study was motivated by the discrepancies in energy transfer predictions using the previously documented coefficients (Bhushan and Warsi, Int. J. Numer. Meth. Fluids 2005; 49 : 489–519). The discrepancies are identified to be due to inconsistent filter functions used in the analytic estimates and the simulations. The study emphasizes that SGS model development should use filter functions compatible with those inherent in CFD application solvers. The dynamic approach predicts consistent model and transfer coefficients for different grid resolutions and is judged to be a reliable basis for model coefficient adjustments. The predicted Leonard's stress coefficient and associated energy transfer coefficients agree very well with the analytic estimates using a Gaussian/cutoff combination filter. This suggests that the modeling of Leonard's stress term using a truncated Taylor series expansion is robust and may not benefit significantly from dynamic modeling. Validation simulations were performed for turbulent channel flow at Re_τ = 180 and 590. The dynamic approach was found to be reliable only for the lower log‐layer of the Re_τ = 590 case, where the scale invariance condition was satisfied. Nonetheless, in this narrow range, the model and transfer coefficients compare well with the isotropic case. The static coefficient algebraic model with new adjusted coefficients shows improved predictions compared with the previous coefficients, for both isotropic decaying turbulence and channel flow cases. Copyright © 2013 John Wiley & Sons, Ltd.     

A comparison of the GWCE and mixed P − P1 formulations in finite‐element linearized shallow‐water models

The appearance of spurious pressure modes in early shallow‐water (SW) models has resulted in two common strategies in the finite element (FE) community: using mixed primitive variable and generalized wave continuity equation (GWCE) formulations of the SW equations. One FE scheme in particular, the P ? P₁ pair, combined with the primitive equations may be advantageously compared with the wave equation formulations and both schemes have similar data structures. Our focus here is on comparing these two approaches for a number of measures including stability, accuracy, efficiency, conservation properties, and consistency. The main part of the analysis centres on stability and accuracy results via Fourier‐based dispersion analyses in the context of the linear SW equations. The numerical solutions of test problems are found to be in good agreement with the analytical results. Copyright © 2011 John Wiley & Sons, Ltd.     

Unexpected higher-order effects in charged particle impact ionization at high energies

Most of the experimental and theoretical studies of electron-impact ionization of atoms, referred to as (e, 2e), have concentrated on the scattering plane. The assumption has been that all the important physical effects will be observable in the scattering plane. However, very recently it has been shown that, for C6+-helium ionization, experiment and theory are in nice agreement in the scattering plane and in very bad agreement out of the scattering plane. This lack of agreement between experiment and theory has been explained in terms of higher-order scattering effects between the projectile and target ion. We have examined electron-impact ionization of magnesium and have observed similar higher-order effects. The results of the electron-impact ionization of magnesium indicate the possible deficiencies in the calculation of fully differential cross sections in previous heavy particle ionization work.     

An XPS study on the attachment of triethoxsilylbutyraldehyde to two titanium surfaces as a way to bond chitosan

A bioactive coating has the ability to create a strong interface between bone tissue and implant. Chitosan, a biopolymer derived from the exoskeletons of shellfish, exhibits many bioactive properties that make it an ideal material for use as a coating such as antibacterial, biodegradable, non-toxic, and the ability to attract and promote bone cell growth and organized bone formation. A previous study reported on the bonding of chitosan to a titanium surface using a three-step process. In the current study, 86.4% de-acetylated chitosan coatings were bound to implant quality titanium in a two-step process that involved the deposition of triethoxsilylbutyraldehyde (TESBA) in toluene, followed by a reaction between the aldehyde of TESBA with chitosan. The chitosan coatings were examined on two different metal treatments to determine if any major differences in the ability of titanium to bind chitosan could be detected. The surface of the titanium metal and the individual reaction steps were examined using X-ray photoelectron spectroscopy (XPS). Following the deposition of TESBA, significant changes were seen in the amounts of oxygen, silicon, carbon, and titanium present on the titanium surface, which were consistent with the anticipated reaction steps. It was demonstrated that more TESBA was bound to the piranha-treated titanium surface as compared to the passivated titanium surface. The two different silane molecules, aminopropyltriethoxysilane (APTES) and TESBA, did not affect the chemistry of the resultant chitosan films. XPS showed that both the formation of unwanted polysiloxanes and the removal of the reactive terminal groups were prevented by using toluene as the carrier solvent to bond TESBA to the titanium surfaces, instead of an aqueous solvent. Qualitatively, the chitosan films demonstrated improved adhesion after using toluene, as the films remained attached to the titanium surface even when placed under the ultra-high vacuum necessary for XPS, unlike the chitosan films deposited using an aqueous solvent, which were removed when exposed to the ultra-high vacuum environment of XPS.     

On the extensional viscosity of mobile polymer solutions

We describe experimental results on the extensional viscosity of mobile polymer solutions obtained from two instruments, the first being a commercial Spin Line Rheometer and the second a custom-built lubricated-die Converging Flow Rheometer. The interpretation of data in terms of Trouton ratios is facilitated by a simple analysis for the Generalized Newtonian Fluid model.Agreement between data from the two rheometers is satisfactory and we show that polymer solutions can be either tension stiffening or tension thinning. However, the Trouton ratios in both cases are greater than the Newtonian values and we anticipate that this will always be the case for polymer solutions.Invited paper, presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986