Classical logic, continuation semantics and abstract machines

One of the goals of this paper is to demonstrate that denotational semantics is useful for operational issues like implementation of functional languages by abstract machines. This is exemplified in a tutorial way by studying the case of extensional untyped call-by-name λ-calculus with Felleisen's control operator 𝒞. We derive the transition rules for an abstract machine from a continuation semantics which appears as a generalization of the ¬¬-translation known from logic. The resulting abstract machine appears as an extension of Krivine's machine implementing head reduction. Though the result, namely Krivine's machine, is well known our method of deriving it from continuation semantics is new and applicable to other languages (as e.g. call-by-value variants). Further new results are that Scott's D∞-models are all instances of continuation models. Moreover, we extend our continuation semantics to Parigot's λμ-calculus from which we derive an extension of Krivine's machine for λμ-calculus. The relation between continuation semantics and the abstract machines is made precise by proving computational adequacy results employing an elegant method introduced by Pitts

Exploring elite soccer teams’ performances during different match-status periods of close matches’ comebacks

The aim of the present study was to examine winning and losing teams’ performances during the four different match-status periods that occur in close soccer matches’ comebacks (1° drawing; 2° winning/losing; 3° drawing; and 4° losing/winning). The variables (i.e., shots, passing effectiveness and ball possession) were gathered from 17 matches of the Spanish professional soccer league. Relative-phase analysis of ball possession between teams revealed a shift from anti-phase to in-phase relations from period 1 to 4. Pass efficacy revealed a particular trend of anti-phase relations in period 2 and the analysis of shots revealed similar phase relations between periods. Statistically significant differences were observed between winning and losing teams in Period 3 for ball possession and passing effectiveness. Also, statistically significant differences among periods were observed for winning teams in ball possession with period 4 as the most differentiated from the other periods. Besides, winning teams also showed significant differences between periods in passing effectiveness (period 4 vs 3), and in shots (period 3 vs periods 1, 2 and 4). On the other hand, ball possession showed significant differences for losing teams with periods 3 and 4 different than periods 1 and 2. The current findings can be used when controlling match-status scenarios and key performance indicators along the match

Where the linearized Poisson-Boltzmann cell model fails: (I) spurious phase separation in charged colloidal suspensions

We perform a linearization of the Poisson-Boltzmann (PB) density functional for spherical Wigner-Seitz cells that yields Debye-H\"uckel-like equations agreeing asymptotically with the PB results in the weak-coupling (high-temperature) limit. Both the canonical (fixed number of microions) as well as the semi-grand-canonical (in contact with an infinite salt reservoir) cases are considered and discussed in a unified linearized framework. In the canonical case, for sufficiently large colloidal charges the linearized theory predicts the occurrence of a thermodynamical instability with an associated phase separation of the homogeneous suspension into dilute (gas) and dense (liquid) phases. In the semi-grand-canonical case it is predicted that the isothermal compressibility and the osmotic-pressure difference between the colloidal suspension and the salt reservoir become negative in the low-temperature, high-surface charge or infinite-dilution (of polyions) limits. As already pointed out in the literature for the latter case, these features are in disagreement with the exact nonlinear PB solution inside a Wigner-Seitz cell and are thus artifacts of the linearization. By using explicitly gauge-invariant forms of the electrostatic potential we show that these artifacts, although thermodynamically consistent with quadratic expansions of the nonlinear functional and osmotic pressure, may be traced back to the non-fulfillment of the underlying assumptions of the linearization.Comment: 32 pages, 3 PostScript figures, submitted to J. Chem. Phy

Dual role of benzophenone enables a fast and scalable C-4 selective alkylation of pyridines in flow

The efficient C-4 selective modification of pyridines is a major challenge for the synthetic community. Current strategies are plagued with at least one drawback regarding functional group-tolerant electronic activation of the heteroarene, mild generation of the required alkyl radicals, regioselectivity, safety and/or scalability. Herein, we describe a fast, safe and scalable flow process which allows preparation of said C-4 alkylated pyridines. The process involves a photochemical hydrogen atom transfer (HAT) event to generate the carbon-centered radicals needed to alkylate the C-2 blocked pyridine. In a two-step streamlined flow process, this light-mediated alkylation step is combined with a nearly instantaneous inline removal of the blocking group. Notably, cheap benzophenone plays a dual role in the pyridine alkylation mechanism by activating the hydrocarbon feedstock reagents via a HAT mechanism, and by acting as a benign, terminal oxidant. The key role of benzophenone in the operative reaction mechanism has also been revealed through a combination of experimental and computational studies

Selenium isotope evidence for pulsed flow of oxidative slab fluids

Isotope systematics of the redox sensitive and chalcophile element selenium (Se) were investigated on exhumed parts of subducted oceanic lithosphere to provide new constraints on slab dehydration conditions during subduction. The samples c,, show increasing delta(82/76)Se(NIST3149 )with higher abundances of fluid mobile elements, comprising a larger range (-1.89 to +0.48 parts per thousand) than that of mantle (-0.13 +/- 0.12 parts per thousand) and altered ocean crust (-0.35 to -0.07 parts per thousand). Our data point to pronounced, local scale redox variations within the subducting crust, wherein oxidative fluids dissolve sulfides and mobilise oxidised Se species. Subsequently recrystallising sulfides preferentially incorporate isotopically lighter, reduced Se, which shifts evolving fluids and late stage sulfides to higher delta Se-82/76(NIST3149). Redistribution of Se by repeated cydes of sulfide reworking within the subducted crust can be reconciled with episodes of oxidised fluid pulses from underlying slab mantle in modem subduction zones