Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge.

Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism

An automatic visual analysis system for tennis

This article presents a novel video analysis system for coaching tennis players of all levels, which uses computer vision algorithms to automatically edit and index tennis videos into meaningful annotations. Existing tennis coaching software lacks the ability to automatically index a tennis match into key events, and therefore, a coach who uses existing software is burdened with time-consuming manual video editing. This work aims to explore the effectiveness of a system to automatically detect tennis events. A secondary aim of this work is to explore the bene- fits coaches experience in using an event retrieval system to retrieve the automatically indexed events. It was found that automatic event detection can significantly improve the experience of using video feedback as part of an instructional coaching session. In addition to the automatic detection of key tennis events, player and ball movements are automati- cally tracked throughout an entire match and this wealth of data allows users to find interesting patterns in play. Player and ball movement information are integrated with the automatically detected tennis events, and coaches can query the data to retrieve relevant key points during a match or analyse player patterns that need attention. This coaching software system allows coaches to build advanced queries, which cannot be facilitated with existing video coaching solutions, without tedious manual indexing. This article proves that the event detection algorithms in this work can detect the main events in tennis with an average precision and recall of 0.84 and 0.86, respectively, and can typically eliminate man- ual indexing of key tennis events

Persistence in Cluster--Cluster Aggregation

Persistence is considered in diffusion--limited cluster--cluster aggregation, in one dimension and when the diffusion coefficient of a cluster depends on its size $s$ as $D(s) \sim s^\gamma$. The empty and filled site persistences are defined as the probabilities, that a site has been either empty or covered by a cluster all the time whereas the cluster persistence gives the probability of a cluster to remain intact. The filled site one is nonuniversal. The empty site and cluster persistences are found to be universal, as supported by analytical arguments and simulations. The empty site case decays algebraically with the exponent $\theta_E = 2/(2 - \gamma)$. The cluster persistence is related to the small $s$ behavior of the cluster size distribution and behaves also algebraically for $0 \le \gamma < 2$ while for $\gamma < 0$ the behavior is stretched exponential. In the scaling limit $t \to \infty$ and $K(t) \to \infty$ with $t/K(t)$ fixed the distribution of intervals of size $k$ between persistent regions scales as $n(k;t) = K^{-2} f(k/K)$, where $K(t) \sim t^\theta$ is the average interval size and $f(y) = e^{-y}$. For finite $t$ the scaling is poor for $k \ll t^z$, due to the insufficient separation of the two length scales: the distances between clusters, $t^z$, and that between persistent regions, $t^\theta$. For the size distribution of persistent regions the time and size dependences separate, the latter being independent of the diffusion exponent $\gamma$ but depending on the initial cluster size distribution.Comment: 14 pages, 12 figures, RevTeX, submitted to Phys. Rev.

The Edinburgh-Cape Blue Object Survey - III. Zone 2; galactic latitudes -30? > b > -40?

The Edinburgh–Cape Blue Object Survey seeks to identify point sources with an ultraviolet excess. Results for zone 2 of the survey are presented here, covering that part of the South Galactic Cap between 30◦ and 40◦ from the Galactic plane and south of about −12. ◦ 3 of declination. Edinburgh–Cape zone 2 comprises 66 UK Schmidt Telescope fields covering about 1730 deg2, in which we find some 892 blue objects, including 423 hot subdwarfs (∼47 per cent); 128 white dwarfs (∼14 per cent); 25 cataclysmic variables (∼3 per cent); 119 binaries (∼13 per cent), mostly composed of a hot subdwarf and a main-sequence F or G star; 66 horizontal branch stars (∼7 per cent) and 48 ‘star-like’ extragalactic objects (∼5 per cent). A further 362 stars observed in the survey, mainly low-metallicity F- and G-type stars, are also listed. Both low-dispersion spectroscopic classification and UBV photometry are presented for almost all of the hot objects and either spectroscopy or photometry (or both) for the cooler ones.Department of HE and Training approved lis

Coaxial Jets and Sheaths in Wide-Angle-Tail Radio Galaxies

We add 20, 6 and 3.6 cm wavelength VLA observations of two WATs, 1231+674 and 1433+553, to existing VLA data at 6 and 20 cm, in order to study the variations of spectral index as a function of position. We apply the spectral tomography process that we introduced in our analysis of 3C67, 3C190 and 3C449. Both spectral tomography and polarization maps indicate that there are two distinct extended components in each source. As in the case of 3C449, we find that each source has a flat spectrum jet surrounded by a steeper spectrum sheath. The steep components tend to be more highly polarized than the flat components. We discuss a number of possibilities for the dynamics of the jet/sheath systems, and the evolution of their relativistic electron populations. While the exact nature of these two coaxial components is still uncertain, their existence requires new models of jets in FR I sources and may also have implications for the dichotomy between FR Is and FR IIs.Comment: 29 text pages plus 13 figures. Scheduled for publication in May 10, 1999 Ap

Triazolium Salt Organocatalysis: Mechanistic Evaluation of Unusual Ortho-Substituent Effects on Deprotonation

Organocatalysis by N-heterocyclic carbenes is normally initiated by the deprotonation of precursor azolium ions to form active nucleophilic species. Substituent effects on deprotonation have an impact on catalytic efficiency and provide insight into general catalytic mechanisms by commonly used azolium systems. Using an NMR kinetic method for the analysis of C(3)-H/D exchange, we determined log kex–pD profiles for three ortho-substituted N-aryl triazolium salts, which enables a detailed analysis of ortho-substituent effects on deprotonation. This includes N-5-methoxypyrid-2-yl triazolium salt 7 and di-ortho-methoxy and di-ortho-isopropoxyphenyl triazolium salts 8 and 9, and we acquired additional kinetic data to supplement our previously published analysis of N-pyrid-2-yl triazolium salt 6. For 2-pyridyl triazoliums 6 and 7, novel acid catalysis of C(3)-H/D exchange is observed under acidic conditions. These kinetic data were supplemented by DFT analyses of the conformational preferences of 6 upon N-protonation. A C(3) deprotonation mechanism involving intramolecular general base deprotonation by the pyridyl nitrogen of the N(1)-deuterated dicationic triazolium salt is most consistent with the data. We also report kDO values (protofugalities) for deuteroxide-catalyzed exchange for 6–9. The protofugalities for 8 and 9 are the lowest values to date in the N-aryl triazolium series

"Remember Everything": things past in Station Island

Book synopsis: Seamus Heaney: Poet, Critic, Translator explores the range of Heaney's writing, emphasizing significant intersections in his work - meeting places; spaces between; tradition meeting the contemporary context as life meets death; liminal poetic representations and political divisions; town and woods, absence and presence; inner reality facing external reality; the timely and the transcendent; region and wider world; Irish tradition encountering Polish tradition; the space between modern English and ancient Greek; the meeting of personal and formal in the translation of Beowulf; different times and perceptions meeting problematic memory; Heaney's Leavisite stance in the face of contemporary critical currents; and Heaney's imagination approaching the imaginations of other poets

Temporal acceleration of a turbulent channel flow

We report new laboratory experiments of a flow accelerating from an initially turbulent state following the opening of a valve, together with large eddy simulations of the experiments and extended Stokes first problem solutions for the early stages of the flow. The results show that the transient flow closely resembles an accelerating laminar flow superimposed on the original steady turbulent flow. The primary consequence of the acceleration is the temporal growth of a boundary layer from the wall, gradually leading to a strong instability causing transition. This extends the findings of previous direct numerical simulations of transient flow following a near-step increase in flow rate. In this interpretation, the initial turbulence is not the primary characteristic of the resulting transient flow, but can be regarded as noise, the evolution of which is strongly influenced by the development of the boundary layer. We observe the spontaneous appearance of turbulent spots and discontinuities in the velocity signals in time and space, revealing rich detail of the transition process, including a striking contrast between streamwise and wall-normal fluctuating velocities

Cluster persistence in one-dimensional diffusion--limited cluster--cluster aggregation

The persistence probability, $P_C(t)$, of a cluster to remain unaggregated is studied in cluster-cluster aggregation, when the diffusion coefficient of a cluster depends on its size $s$ as $D(s) \sim s^\gamma$. In the mean-field the problem maps to the survival of three annihilating random walkers with time-dependent noise correlations. For $\gamma \ge 0$ the motion of persistent clusters becomes asymptotically irrelevant and the mean-field theory provides a correct description. For $\gamma < 0$ the spatial fluctuations remain relevant and the persistence probability is overestimated by the random walk theory. The decay of persistence determines the small size tail of the cluster size distribution. For $0 < \gamma < 2$ the distribution is flat and, surprisingly, independent of $\gamma$.Comment: 11 pages, 6 figures, RevTeX4, submitted to Phys. Rev.